JP4727238B2 - Optical member pressure-sensitive adhesive composition, optical member pressure-sensitive adhesive layer, pressure-sensitive adhesive optical member, and image display device - Google Patents

Optical member pressure-sensitive adhesive composition, optical member pressure-sensitive adhesive layer, pressure-sensitive adhesive optical member, and image display device Download PDF

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JP4727238B2
JP4727238B2 JP2005016933A JP2005016933A JP4727238B2 JP 4727238 B2 JP4727238 B2 JP 4727238B2 JP 2005016933 A JP2005016933 A JP 2005016933A JP 2005016933 A JP2005016933 A JP 2005016933A JP 4727238 B2 JP4727238 B2 JP 4727238B2
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sensitive adhesive
pressure
optical member
weight
adhesive composition
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JP2006206639A (en
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文明 白藤
正之 佐竹
浩平 矢野
裕 諸石
史子 中野
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Nitto Denko Corp
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Priority to JP2005016933A priority Critical patent/JP4727238B2/en
Priority to US11/814,775 priority patent/US8389611B2/en
Priority to KR1020077019034A priority patent/KR101077810B1/en
Priority to CN2006800025411A priority patent/CN101107547B/en
Priority to PCT/JP2006/300131 priority patent/WO2006080185A1/en
Priority to TW095101604A priority patent/TW200639227A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08Homopolymers or copolymers of acrylic acid esters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Description

本発明は光学部材用粘着剤組成物に関する。また本発明は当該光学部材用粘着剤組成物により形成される光学部材用粘着剤層に関する。さらに本発明は、当該粘着剤層を有する粘着型光学部材、前記粘着型光学部材を用いた液晶表示装置、有機EL表示装置、PDP等の画像表示装置に関する。前記光学部材としては、偏光板、位相差板、光学補償フィルム、輝度向上フィルム、さらにはこれらが積層されているものなどがあげられる。   The present invention relates to a pressure-sensitive adhesive composition for optical members. Moreover, this invention relates to the adhesive layer for optical members formed with the said adhesive composition for optical members. Furthermore, the present invention relates to an adhesive optical member having the adhesive layer, a liquid crystal display device using the adhesive optical member, an organic EL display device, and an image display device such as a PDP. Examples of the optical member include a polarizing plate, a retardation plate, an optical compensation film, a brightness enhancement film, and those in which these are laminated.

光学部材用に用いられる粘着剤層は、その厚みや表面均一性が高いレベルで要求される。そのため、ポリマー濃度を低くしてポリマー組成物の粘度を低下させて塗工している。しかし、環境への配慮から有機溶媒の使用量をできるだけ低減したいのが実状である。   The pressure-sensitive adhesive layer used for an optical member is required to have a high level of thickness and surface uniformity. Therefore, the coating is carried out by lowering the polymer concentration to reduce the viscosity of the polymer composition. However, the actual situation is to reduce the amount of organic solvent used as much as possible in consideration of the environment.

有機溶媒を使用しない方法として、エマルション粘着剤やUV重合タイプの粘着剤があるが、耐水性の問題や厚みの均一性など光学部材用に用いるまでに至っていない。   As methods that do not use an organic solvent, there are emulsion adhesives and UV polymerization type adhesives, but they have not yet been used for optical members such as water resistance problems and uniformity of thickness.

ポリマー濃度を高くした場合でも、ポリマー溶液の粘度が上がらないようにする方法としては、ポリマーの分子量を小さくする方法が挙げられる。しかし、液晶表示装置等に用いる光学部材、例えば、偏光板や位相差板などは液晶セルに粘着剤を介して貼り付けられているが、加熱条件下や加湿条件下では光学部材の膨張、収縮が発生するため、貼り付け後にはそれに伴う浮きや剥がれが生じやすい。ポリマーの分子量が小さい場合には、加熱条件下や加湿条件下における浮きや剥がれが発生しやすいため、ポリマーの分子量を小さくすることは困難である。   As a method for preventing the viscosity of the polymer solution from increasing even when the polymer concentration is increased, a method for reducing the molecular weight of the polymer can be mentioned. However, optical members used in liquid crystal display devices, such as polarizing plates and retardation plates, are attached to liquid crystal cells via an adhesive, but the expansion and contraction of optical members under heating and humidification conditions. Therefore, after sticking, the floating and peeling accompanying it are likely to occur. When the molecular weight of the polymer is small, it is difficult to reduce the molecular weight of the polymer because it tends to float and peel off under heating and humidification conditions.

高温多湿条件下においても優れた粘着性を維持し、寸法変化に伴う発泡や剥がれ等の発生を防止することを目的として、特定の数種の(メタ)アクリル系ポリマーと架橋剤を含有する偏光板用粘着剤組成物が開示されている(特許文献1)。   Polarized light containing several specific (meth) acrylic polymers and a cross-linking agent for the purpose of maintaining excellent adhesion even under high temperature and high humidity conditions and preventing the occurrence of foaming and peeling due to dimensional changes. An adhesive composition for a plate is disclosed (Patent Document 1).

また、高温下又は高温高湿下でも凝集力及び接着力の経時変化を小さくすることを目的として、アクリル系樹脂中に、硬化剤及び、特定のシラン系化合物を配合した粘着剤組成物が開示されている(特許文献2)。   Also disclosed is a pressure-sensitive adhesive composition in which a curing agent and a specific silane compound are blended in an acrylic resin for the purpose of reducing the temporal change of cohesive force and adhesive force even under high temperature or high temperature and high humidity. (Patent Document 2).

しかしながら、これら従来の粘着剤組成物では、有機溶媒使用量の削減と形成される粘着剤層の高い表面均一性とを共に満たすことはできない。
特開2003−49141号公報 特開平8−199131号公報
However, these conventional pressure-sensitive adhesive compositions cannot satisfy both the reduction in the amount of organic solvent used and the high surface uniformity of the formed pressure-sensitive adhesive layer.
JP 2003-49141 A JP-A-8-199131

本発明は、粘度が小さいため塗工性がよく、有機溶媒使用量の削減が可能であり、さらに耐久性に優れかつ表面均一性の高い粘着剤層を形成することのできる光学部材用粘着剤組成物を提供することを目的とする。また本発明は、該光学部材用粘着剤組成物により形成される光学部材用粘着剤層を提供することを目的とする。さらに本発明は、該粘着剤層を有する粘着型光学部材を提供すること、及び該粘着型光学部材を用いた画像表示装置を提供することを目的とする。   The present invention is a pressure-sensitive adhesive for optical members that has good coating properties due to low viscosity, can reduce the amount of organic solvent used, and can form a pressure-sensitive adhesive layer with excellent durability and high surface uniformity. An object is to provide a composition. Moreover, an object of this invention is to provide the adhesive layer for optical members formed with this adhesive composition for optical members. Furthermore, an object of this invention is to provide the adhesive optical member which has this adhesive layer, and to provide the image display apparatus using this adhesive optical member.

本発明者らは、上記課題を達成すべく鋭意検討した結果、下記光学部材用粘着剤組成物等により上記目的を達成できることを見出し、本発明を完成するに至った。   As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the above-described object can be achieved by the following pressure-sensitive adhesive composition for optical members, and have completed the present invention.

すなわち本発明は、(メタ)アクリル系ポリマー、炭素数6〜9の炭化水素系溶媒(A)、及び前記炭化水素系溶媒よりも沸点が高くかつ前記炭化水素系溶媒よりも(メタ)アクリル系ポリマーの溶解性が高い高沸点高溶解性溶媒(B)を含有しており、前記炭化水素系溶媒(A)の含有量が全有機溶媒の20〜60重量%であり、かつ前記高沸点高溶解性溶媒(B)の含有量(重量%)に対する前記炭化水素系溶媒(A)の含有量(重量%)の比(高沸点高溶解性溶媒(B)/炭化水素系溶媒(A))が0.05〜4である光学部材用粘着剤組成物、に関する。   That is, the present invention provides a (meth) acrylic polymer, a hydrocarbon solvent having 6 to 9 carbon atoms (A), and a boiling point higher than that of the hydrocarbon solvent and (meth) acrylic than that of the hydrocarbon solvent. A high-boiling high-solubility solvent (B) having a high polymer solubility, the content of the hydrocarbon solvent (A) is 20 to 60% by weight of the total organic solvent, and the high-boiling high Ratio of the content (% by weight) of the hydrocarbon solvent (A) to the content (% by weight) of the soluble solvent (B) (high boiling point high solubility solvent (B) / hydrocarbon solvent (A)) Relates to a pressure-sensitive adhesive composition for an optical member having a thickness of 0.05 to 4.

本発明の光学部材用粘着剤組成物は、(メタ)アクリル系ポリマーを溶解する溶媒として、上記2種の溶媒を併用することにより、該光学部材用粘着剤組成物からなる粘着剤層を有する光学部材を液晶セル等に貼り合わせた後に、加熱条件下や加湿条件下に曝された場合であっても粘着剤層の浮きや剥がれを防止することができる。さらに、粘度が小さいため塗工性がよく、粘着剤組成物中の有機溶媒の含有量を削減しつつ、形成される粘着剤層の表面均一性を高く維持することができる。   The pressure-sensitive adhesive composition for optical members of the present invention has a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for optical members by using the two kinds of solvents in combination as a solvent for dissolving the (meth) acrylic polymer. Even after the optical member is bonded to a liquid crystal cell or the like, the pressure-sensitive adhesive layer can be prevented from being lifted or peeled even when exposed to heating conditions or humidification conditions. Furthermore, since the viscosity is small, the coating property is good, and the surface uniformity of the formed pressure-sensitive adhesive layer can be kept high while reducing the content of the organic solvent in the pressure-sensitive adhesive composition.

このように、上記2種の溶媒を併用することによりこれらの効果が発現する理由は明らかではないが以下の理由が考えられる。炭化水素系溶媒(A)を用いることにより、(メタ)アクリル系ポリマーの高分子ドメインを収縮させることができる。そのため粘着剤組成物の粘度を低下させることができるが、該溶媒のみを用いた場合には、塗工、乾燥の際にポリマーが析出して粘着剤層の表面均一性が著しく低下したり、ポリマーが析出することにより分子鎖間の絡み合いが不十分になって加熱条件下や加湿条件下で粘着剤層の浮きや剥がれが発生しやすくなる。しかし、高沸点高溶解性溶媒(B)を併用することにより、粘着剤組成物の塗工及び乾燥時において、高沸点高溶解性溶媒(B)は炭化水素系溶媒(A)よりも遅れて揮発するため、粘着剤組成物中のポリマーが析出することを効果的に抑制することができ、形成される粘着剤層の表面均一性は高く維持されると考えられる。また、高沸点高溶解性溶媒(B)は、ポリマーの溶解性が高いため、高分子ドメインが膨張し、分子鎖間の絡み合いが多くなり、さらには分子鎖間の架橋も均一に進行する。そのため加熱条件下や加湿条件下に曝された場合であっても粘着剤層の浮きや剥がれを防止することができると考えられる。   Thus, although the reason why these effects are manifested by using the two kinds of solvents in combination is not clear, the following reasons can be considered. By using the hydrocarbon solvent (A), the polymer domain of the (meth) acrylic polymer can be contracted. Therefore, the viscosity of the pressure-sensitive adhesive composition can be reduced, but when only the solvent is used, the surface uniformity of the pressure-sensitive adhesive layer is significantly reduced due to precipitation of a polymer during coating and drying, When the polymer is precipitated, the entanglement between the molecular chains becomes insufficient, and the pressure-sensitive adhesive layer easily floats or peels off under heating or humidification conditions. However, by using the high-boiling high-solubility solvent (B) in combination, the high-boiling high-solubility solvent (B) is delayed from the hydrocarbon solvent (A) at the time of coating and drying the pressure-sensitive adhesive composition. Since it volatilizes, it can suppress effectively that the polymer in an adhesive composition precipitates, and it is thought that the surface uniformity of the adhesive layer formed maintains high. In addition, since the high-boiling and high-solubility solvent (B) has high polymer solubility, the polymer domain expands, entanglement between molecular chains increases, and cross-linking between molecular chains also proceeds uniformly. Therefore, it is considered that the pressure-sensitive adhesive layer can be prevented from being lifted or peeled even when exposed to heating conditions or humidification conditions.

本発明において、炭化水素系溶媒(A)の含有量は全有機溶媒の20〜60重量%にする必要がある。20重量%未満の場合には、粘着剤組成物の粘度低下効果が小さく、有機溶媒の使用量を削減することが困難になる。一方、60重量%を超える場合には、塗工、乾燥時に(メタ)アクリル系ポリマーが析出して粘着剤層の表面均一性が著しく低下したり、ポリマーが析出することにより分子鎖間の絡み合いが不十分になって加熱条件下や加湿条件下で粘着剤層の浮きや剥がれが発生しやすくなる。   In the present invention, the content of the hydrocarbon solvent (A) needs to be 20 to 60% by weight of the total organic solvent. If it is less than 20% by weight, the effect of reducing the viscosity of the pressure-sensitive adhesive composition is small, and it becomes difficult to reduce the amount of organic solvent used. On the other hand, when the amount exceeds 60% by weight, the (meth) acrylic polymer is precipitated during coating and drying, and the surface uniformity of the pressure-sensitive adhesive layer is remarkably reduced, or the polymer is precipitated, thereby entanglement between molecular chains. Becomes insufficient, and the pressure-sensitive adhesive layer easily floats or peels off under heating or humidification conditions.

また本発明においては、高沸点高溶解性溶媒(B)の含有量(重量%)に対する炭化水素系溶媒(A)の含有量(重量%)の比(高沸点高溶解性溶媒(B)/炭化水素系溶媒(A))が0.05〜4であることが必要である。比が0.05未満の場合には、粘着剤組成物を塗工、乾燥する際にポリマーが析出して粘着剤層の表面均一性が著しく低下したり、ポリマーが析出することにより分子鎖間の絡み合いが不十分になって加熱条件下や加湿条件下で粘着剤層の浮きや剥がれが発生する。一方、比が4を越える場合には、上記溶媒を十分に乾燥除去することが困難になり耐久性等の粘着特性が低下する。   In the present invention, the ratio of the content (% by weight) of the hydrocarbon solvent (A) to the content (% by weight) of the high boiling point high solubility solvent (B) (the high boiling point high solubility solvent (B) / The hydrocarbon solvent (A)) needs to be 0.05-4. When the ratio is less than 0.05, when the pressure-sensitive adhesive composition is applied and dried, the polymer precipitates and the surface uniformity of the pressure-sensitive adhesive layer is remarkably reduced, or the polymer is precipitated to cause intermolecular chains. The entanglement of the adhesive layer becomes insufficient, and the pressure-sensitive adhesive layer is lifted or peeled off under heating or humidification conditions. On the other hand, when the ratio exceeds 4, it is difficult to sufficiently dry and remove the solvent, and the adhesive properties such as durability are deteriorated.

また本発明において、前記(メタ)アクリル系ポリマーは、モノマーとして炭素数2〜4のアルキル基を有するアクリル酸アルキルを60重量%以上含有してなり、重量平均分子量が150万以上であり、かつ分子量10万以下のポリマー成分の含有率が20重量%以下であることが好ましい。また、前記(メタ)アクリル系ポリマーは、さらに、モノマーとして不飽和カルボン酸を0.2〜7重量%含有してなることが好ましい。   In the present invention, the (meth) acrylic polymer contains 60% by weight or more of an alkyl acrylate having an alkyl group having 2 to 4 carbon atoms as a monomer, has a weight average molecular weight of 1,500,000 or more, and The content of the polymer component having a molecular weight of 100,000 or less is preferably 20% by weight or less. The (meth) acrylic polymer preferably further contains 0.2 to 7% by weight of an unsaturated carboxylic acid as a monomer.

本発明の光学部材用粘着剤組成物は、(メタ)アクリル系ポリマー100重量部に対して、シランカップリング剤を0.01〜1重量部含有することが好ましい。また、(メタ)アクリル系ポリマー100重量部に対して、架橋剤を0.1〜5重量部含有することが好ましい。シランカップリング剤や架橋剤を含有する粘着剤組成物により形成される架橋構造を有する粘着剤層は、光学部材を液晶セルに貼付け後、各種の工程を経るなどの長時間を経過したり、高温高湿状態で保存されても、接着状態では剥がれ、浮き、発泡などが抑制され耐久性に優れている。   The pressure-sensitive adhesive composition for optical members of the present invention preferably contains 0.01 to 1 part by weight of a silane coupling agent with respect to 100 parts by weight of the (meth) acrylic polymer. Moreover, it is preferable to contain 0.1-5 weight part of crosslinking agents with respect to 100 weight part of (meth) acrylic-type polymers. The pressure-sensitive adhesive layer having a cross-linked structure formed by a pressure-sensitive adhesive composition containing a silane coupling agent or a cross-linking agent passes a long time such as passing through various steps after the optical member is attached to the liquid crystal cell, Even when stored in a high temperature and high humidity state, peeling, floating, foaming and the like are suppressed in the bonded state, and the durability is excellent.

本発明は、前記光学部材用粘着剤組成物から形成される光学部材用粘着剤層、に関する。   The present invention relates to an optical member pressure-sensitive adhesive layer formed from the optical member pressure-sensitive adhesive composition.

また本発明は、光学部材の片面または両面に前記光学部材用粘着剤層を有する粘着型光学部材、に関する。   The present invention also relates to an adhesive optical member having the optical member pressure-sensitive adhesive layer on one or both surfaces of the optical member.

さらに本発明は、前記粘着型光学部材を少なくとも1つ用いた画像表示装置、に関する。   Furthermore, the present invention relates to an image display device using at least one of the adhesive optical members.

本発明の光学部材用粘着剤組成物は、(メタ)アクリル系ポリマー、炭素数6〜9の炭化水素系溶媒(A)、及び前記炭化水素系溶媒よりも沸点が高くかつ前記炭化水素系溶媒よりも(メタ)アクリル系ポリマーの溶解性が高い高沸点高溶解性溶媒(B)を主成分とする。なお、本発明において、(メタ)アクリル系ポリマーはアクリル系ポリマーおよび/またはメタクリル系ポリマーをいう。(メタ)は全て同様の意味である。   The pressure-sensitive adhesive composition for an optical member of the present invention comprises a (meth) acrylic polymer, a hydrocarbon solvent having 6 to 9 carbon atoms (A), and a boiling point higher than that of the hydrocarbon solvent and the hydrocarbon solvent. The main component is a high-boiling high-solubility solvent (B) in which the solubility of the (meth) acrylic polymer is higher. In the present invention, the (meth) acrylic polymer refers to an acrylic polymer and / or a methacrylic polymer. (Meta) has the same meaning.

本発明で使用する(メタ)アクリル系ポリマーは特に制限されないが、ガラス転移点の低さや弾性率の観点から炭素数2〜4のアルキル基を有する(メタ)アクリル酸アルキルのホモポリマーやコポリマー、又はそれらの混合物であることが好ましい。アルキル基の炭素数は3〜4であることがより好ましい。また、アルキル基は、直鎖または分岐鎖のいずれも使用できる。   The (meth) acrylic polymer used in the present invention is not particularly limited, but a homopolymer or copolymer of an alkyl (meth) acrylate having an alkyl group having 2 to 4 carbon atoms from the viewpoint of low glass transition point and elastic modulus, Or it is preferable that they are mixtures. It is more preferable that the alkyl group has 3 to 4 carbon atoms. The alkyl group can be either linear or branched.

前記(メタ)アクリル系ポリマーは、粘着特性の観点から、モノマー単位として炭素数2〜4のアルキル基を有する(メタ)アクリル酸アルキルを60重量%以上含有することが好ましく、より好ましくは70重量%以上である。   The (meth) acrylic polymer preferably contains 60% by weight or more, more preferably 70% by weight of alkyl (meth) acrylate having a C2-C4 alkyl group as a monomer unit from the viewpoint of adhesive properties. % Or more.

また、前記(メタ)アクリル系ポリマーは、粘着特性を調整するために、不飽和カルボン酸を共重合したものであってもよい。   The (meth) acrylic polymer may be a copolymer of an unsaturated carboxylic acid in order to adjust the adhesive properties.

不飽和カルボン酸としては、たとえば、アクリル酸、メタクリル酸、イタコン酸、マレイン酸などがあげられる。これらの無水物を用いることもできる。これらの中でも特にアクリル酸とメタクリル酸が好ましく用いられる。   Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid and the like. These anhydrides can also be used. Of these, acrylic acid and methacrylic acid are particularly preferably used.

前記(メタ)アクリル系ポリマーは、モノマー単位として不飽和カルボン酸を0.2〜7重量%含有することが好ましく、より好ましくは0.5〜5重量%である。不飽和カルボン酸の含有量が0.2重量%未満の場合には耐久性が低下し、7重量%を超える場合には液晶セルへの接着力が大きくなったり、硬くなりすぎるため好ましくない。   The (meth) acrylic polymer preferably contains 0.2 to 7% by weight of unsaturated carboxylic acid as a monomer unit, more preferably 0.5 to 5% by weight. When the content of the unsaturated carboxylic acid is less than 0.2% by weight, the durability is lowered, and when it exceeds 7% by weight, the adhesive force to the liquid crystal cell becomes too large or too hard.

前記(メタ)アクリル系ポリマーは上記以外の他のモノマーを含有していてもよい。他のモノマーとしては、たとえば、ペンチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、ラウリル(メタ)アクリレート等の炭素数5以上のアルキル基を有する(メタ)アクリル酸アルキル;2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、ヒドロキシブチル(メタ)アクリレート、ヒドロキシヘキシル(メタ)アクリレート、N−メチロール(メタ)アクリルアミド等の水酸基を有するモノマー;グリシジル(メタ)アクリレート等エポキシ基を含有するモノマー;(メタ)アクリルアミド、N,N−ジメチル(メタ)アクリルアミド、N,N−ジエチル(メタ)アクリルアミド、(メタ)アクリロイルモルホリン、(メタ)アセトニトリル、ビニルピロリドン、N−シクロヘキシルマレイミド、イタコンイミド、N,N−ジメチルアミノエチル(メタ)アクリルアミド等のN元素を有するモノマー等があげられる。さらには酢酸ビニル、スチレン等を用いることもできる。これらモノマーは1種または2種以上を組み合わせることができる。   The (meth) acrylic polymer may contain a monomer other than the above. Examples of other monomers include alkyl (meth) acrylates having an alkyl group having 5 or more carbon atoms such as pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, and the like; 2 Monomers having a hydroxyl group such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, N-methylol (meth) acrylamide; glycidyl (meth) acrylate Monomers containing an epoxy group such as: (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, (meth) acryloylmorpholine, (meth) acetonitrile, vinyl Rupiroridon, N- cyclohexyl maleimide, itaconimide, N, monomers having N- dimethylaminoethyl (meth) N elements acrylamide and the like. Furthermore, vinyl acetate, styrene, etc. can also be used. These monomers can be used alone or in combination of two or more.

前記(メタ)アクリル系ポリマーの重量平均分子量(GPCにより測定)は150万以上であることが好ましく、より好ましくは200万以上である。重量平均分子量が150万未満の場合には、粘着剤層の耐久性が乏しくなる傾向にある。また、前記(メタ)アクリル系ポリマーは分子量10万以下のポリマー成分の割合が、20重量%以下であることが好ましく、より好ましくは10重量%以下である。本発明においては、炭素数6〜9の炭化水素系溶媒(A)を用いて高分子鎖の絡み合いを小さくしているため、低分子量ポリマー成分が多いとポリマー分子鎖間の架橋性が非常に悪くなる。したがって、低分子量ポリマー成分は少ないほどよい。   The weight average molecular weight (measured by GPC) of the (meth) acrylic polymer is preferably 1.5 million or more, more preferably 2 million or more. When the weight average molecular weight is less than 1,500,000, the durability of the pressure-sensitive adhesive layer tends to be poor. In the (meth) acrylic polymer, the proportion of the polymer component having a molecular weight of 100,000 or less is preferably 20% by weight or less, more preferably 10% by weight or less. In the present invention, since the entanglement of the polymer chain is reduced by using the hydrocarbon solvent (A) having 6 to 9 carbon atoms, if there are many low molecular weight polymer components, the crosslinkability between the polymer molecular chains is very high. Deteriorate. Therefore, the lower the low molecular weight polymer component, the better.

前記(メタ)アクリル系ポリマーの製造は、溶液重合、塊状重合、乳化重合などの公知のラジカル重合法を適宜選択できるが、有機溶剤を用いたラジカル重合法が好ましい。乳化重合のような水を使用した重合法は、一度水を乾燥させてから本発明の溶媒と混合する必要があるため経済的に不利である。ラジカル重合開始剤としては、アゾ系、過酸化物系の各種公知のものを使用できる。例えば、溶液重合では、アゾビスイソブチロニトリルなどの重合開始剤を、モノマー全量100重量部に対し0.01〜0.2重量部程度使用する。重合溶媒としては、たとえば、酢酸エチル、トルエン等の良溶媒が用いられる。反応は窒素等の不活性ガス気流下で、通常、50〜70℃程度で、8〜15時間程度行われる。   For the production of the (meth) acrylic polymer, known radical polymerization methods such as solution polymerization, bulk polymerization, and emulsion polymerization can be selected as appropriate, but radical polymerization using an organic solvent is preferred. A polymerization method using water such as emulsion polymerization is economically disadvantageous because it is necessary to dry the water once and then mix it with the solvent of the present invention. As the radical polymerization initiator, various known azo and peroxide initiators can be used. For example, in solution polymerization, a polymerization initiator such as azobisisobutyronitrile is used in an amount of about 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the total amount of monomers. As the polymerization solvent, for example, a good solvent such as ethyl acetate or toluene is used. The reaction is usually carried out at about 50 to 70 ° C. for about 8 to 15 hours under an inert gas stream such as nitrogen.

本発明では、有機溶媒として、炭素数6〜9の炭化水素系溶媒(A)、及び前記炭化水素系溶媒よりも沸点が高くかつ前記炭化水素系溶媒よりも(メタ)アクリル系ポリマーの溶解性が高い高沸点高溶解性溶媒(B)を併用することが必要である。   In the present invention, as the organic solvent, the hydrocarbon solvent (A) having 6 to 9 carbon atoms, and the solubility of the (meth) acrylic polymer is higher than the hydrocarbon solvent and higher than the hydrocarbon solvent. It is necessary to use a high-boiling and high-solubility solvent (B) having a high value.

前記炭化水素系溶媒(A)の炭素数は6〜8であることが好ましい。炭素数5以下の炭化水素系溶媒は沸点が低すぎるため塗工安定性に欠ける。一方、炭素数10以上の炭化水素系溶媒は沸点が高すぎるため、乾燥後の粘着剤層中に該溶媒が残存して耐久性等の粘着特性が低下する傾向にある。   The hydrocarbon solvent (A) preferably has 6 to 8 carbon atoms. A hydrocarbon solvent having 5 or less carbon atoms has a low boiling point and thus lacks coating stability. On the other hand, since the hydrocarbon solvent having 10 or more carbon atoms has a boiling point that is too high, the solvent remains in the pressure-sensitive adhesive layer after drying, and the adhesive properties such as durability tend to decrease.

炭素数6〜9の炭化水素系溶媒(A)は、直鎖状、分岐鎖状、及び環状のいずれの炭化水素でもよく、具体的には、3−メチルペンタン、ノルマルへキサン、2,4−ジメチルペンタン、2,2,3−トリメチルブタン、3,3−ジメチルペンタン、2−メチルへキサン、2,3−ジメチルペンタン、3−メチルへキサン、ノルマルヘプタン、シクロヘキサン、メチルシクロへキサン、2,2−ジメチルへキサン、2,3−ジメチルへキサン、2,5−ジメチルへキサン、2,4−ジメチルへキサン、3,3−ジメチルへキサン、3,4−ジメチルへキサン、2,3,4−トリメチルペンタン、2,3,3−トリメチルペンタン、2−メチル−3−エチルペンタン、2−メチルヘプタン、3−メチルヘプタン、4−メチルヘプタン、2,2,5−トリメチルへキサン、ノルマルオクタン、シクロオクタン、ノナン、及びシクロノナンなどが挙げられる。これらは1種単独で用いてもよく、2種以上を併用してもよい。また、これらを含む溶剤を使用してもよく、具体的にはカクタスソルベント(ジャパンエナジー社製)が挙げられる。   The hydrocarbon solvent (A) having 6 to 9 carbon atoms may be any of linear, branched, and cyclic hydrocarbons, specifically, 3-methylpentane, normal hexane, 2,4 -Dimethylpentane, 2,2,3-trimethylbutane, 3,3-dimethylpentane, 2-methylhexane, 2,3-dimethylpentane, 3-methylhexane, normal heptane, cyclohexane, methylcyclohexane, 2, 2-dimethyl hexane, 2,3-dimethyl hexane, 2,5-dimethyl hexane, 2,4-dimethyl hexane, 3,3-dimethyl hexane, 3,4-dimethyl hexane, 2,3, 4-trimethylpentane, 2,3,3-trimethylpentane, 2-methyl-3-ethylpentane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,2, - hexane trimethyl, normal octane, cyclooctane, nonane, and cyclononane and the like. These may be used alone or in combination of two or more. Moreover, you may use the solvent containing these, Specifically, Cactus solvent (made by Japan Energy) is mentioned.

光学部材用粘着剤組成物中の炭化水素系溶媒(A)の含有量は、使用する全有機溶媒の20〜60重量%であり、好ましくは35〜55重量%であり、より好ましくは40〜50重量%である。   The content of the hydrocarbon solvent (A) in the pressure-sensitive adhesive composition for optical members is 20 to 60% by weight, preferably 35 to 55% by weight, more preferably 40 to 40% by weight of the total organic solvent to be used. 50% by weight.

高沸点高溶解性溶媒(B)は、前記炭化水素系溶媒(A)よりも沸点が高くかつ前記炭化水素系溶媒(A)よりも(メタ)アクリル系ポリマーの溶解性が高い有機溶媒であれば特に制限されないが、炭化水素系溶媒(A)より沸点が5℃以上高いことが好ましい。また、高沸点高溶解性溶媒(B)は、高沸点高溶解性溶媒(B)の溶解度パラメータθ1〔(cal/cm1/2〕と(メタ)アクリル系ポリマーの溶解度パラメータθ2〔(cal/cm1/2〕との差であるΔθ(Δθ=θ1−θ2)が0.8以下となるものを選択することが好ましく、より好ましくは0.5以下、特に好ましくは0.3以下となるものである。溶解度パラメータは、例えば、Wiley Interscienceから出版されているPolymer Handbook 第3版に記載されている。 The high boiling point high solubility solvent (B) may be an organic solvent having a higher boiling point than the hydrocarbon solvent (A) and a higher solubility of the (meth) acrylic polymer than the hydrocarbon solvent (A). Although it will not restrict | limit in particular, It is preferable that a boiling point is 5 degreeC or more higher than a hydrocarbon type solvent (A). The high-boiling and high-solubility solvent (B) includes a solubility parameter θ1 [(cal / cm 3 ) 1/2 ] of the high-boiling and high-solubility solvent (B) and a solubility parameter θ2 [(()) of the (meth) acrylic polymer. cal / cm 3 ) 1/2 ] is preferably selected such that Δθ (Δθ = θ1−θ2) is 0.8 or less, more preferably 0.5 or less, particularly preferably 0.8. 3 or less. Solubility parameters are described, for example, in Polymer Handbook 3rd edition published by Wiley Interscience.

本発明において用いられる高沸点高溶解性溶媒(B)としては、例えば、トルエン及びキシレンなどの芳香族炭化水素系溶媒;酢酸エチル及び酢酸ブチルなどの脂肪族カルボン酸エステル系溶媒;メチルエチルケトン及びエチルブチルケトンなどのケトン系溶媒などが挙げられる。高沸点高溶解性溶媒(B)は、炭化水素系溶媒(A)との関係で上記条件を満たすものを適宜選択する必要がある。   Examples of the high-boiling and high-solubility solvent (B) used in the present invention include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic carboxylic acid ester solvents such as ethyl acetate and butyl acetate; methyl ethyl ketone and ethyl butyl Examples thereof include ketone solvents such as ketones. As the high boiling point high solubility solvent (B), it is necessary to appropriately select a solvent satisfying the above conditions in relation to the hydrocarbon solvent (A).

本発明においては、高沸点高溶解性溶媒(B)の含有量(重量%)に対する炭化水素系溶媒(A)の含有量(重量%)の比(高沸点高溶解性溶媒(B)/炭化水素系溶媒(A))が0.05〜4であり、好ましくは0.05〜1.86であり、より好ましくは0.2〜0.75である。   In the present invention, the ratio of the content (wt%) of the hydrocarbon solvent (A) to the content (wt%) of the high boiling high solubility solvent (B) (high boiling high solubility solvent (B) / carbonization). The hydrogen-based solvent (A)) is 0.05 to 4, preferably 0.05 to 1.86, more preferably 0.2 to 0.75.

本発明の光学部材用粘着剤組成物は、シランカップリング剤や架橋剤を含有することが好ましい。   The pressure-sensitive adhesive composition for optical members of the present invention preferably contains a silane coupling agent or a crosslinking agent.

シランカップリング剤としては、従来より知られているものを特に制限なく使用できる。たとえば、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルメチルジエトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシランなどのエポキシ基含有シランカップリング剤;3−アミノプロピルトリメトキシシラン、N−2−(アミノエチル)−3−アミノプロピルメチルジメトキシシラン、3−トリエトキシシリル−N−(1,3−ジメチルブチリデン)プロピルアミンなどのアミノ基含有シランカップリング剤;3−アクリロキシプロピルトリメトキシシラン、3−メタクリロキシプロピルトリエトキシシランなどの(メタ)アクリル基含有シランカップリング剤;3−イソシアネートプロピルトリエトキシシランなどのイソシアネート基含有シランカップリング剤などがあげられる。   As the silane coupling agent, those conventionally known can be used without particular limitation. For example, epoxy group-containing silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-amino Amino group-containing silane coupling agents such as propyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine ; (Meth) acryl group-containing silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane; isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane Is .

シランカップリング剤の添加量は、(メタ)アクリル系ポリマー100重量部に対して、0.01〜1重量部であることが好ましく、より好ましくは0.02〜0.6重量部である。シランカップリング剤の添加量が、1重量部を超えると液晶セルへの接着力が増大して再剥離性に劣るので好ましくなく、0.01重量部未満では耐久性が低下するため好ましくない。   It is preferable that the addition amount of a silane coupling agent is 0.01-1 weight part with respect to 100 weight part of (meth) acrylic-type polymers, More preferably, it is 0.02-0.6 weight part. If the addition amount of the silane coupling agent exceeds 1 part by weight, the adhesive strength to the liquid crystal cell increases and the removability is inferior.

架橋剤は、(メタ)アクリル系ポリマーと反応して架橋構造を形成できる多官能化合物である。架橋剤としては、たとえば、トリレンジイソシアネート、ジフェニルメタンジイソシアネートなどのジイソシアネート化合物を各種ポリオールへ付加したポリイソシアネート化合物、エポキシ化合物、アジリジン化合物、メラミン化合物、金属塩、金属キレート化合物などがあげられる。これらのなかでも、ポリイソシアネート化合物が好ましく用いられる。特に、(メタ)アクリル系ポリマーの製造時に、2−ヒドロキシエチルアクリレートなどの水酸基含有モノマーを共重合して(メタ)アクリル系ポリマーに水酸基を導入した場合には、架橋剤としてポリイソシアネート化合物を使用して架橋構造を形成するのが好適である。   The crosslinking agent is a polyfunctional compound that can react with the (meth) acrylic polymer to form a crosslinked structure. Examples of the crosslinking agent include polyisocyanate compounds obtained by adding diisocyanate compounds such as tolylene diisocyanate and diphenylmethane diisocyanate to various polyols, epoxy compounds, aziridine compounds, melamine compounds, metal salts, metal chelate compounds, and the like. Of these, polyisocyanate compounds are preferably used. In particular, when a hydroxyl group is introduced into a (meth) acrylic polymer by copolymerizing a hydroxyl group-containing monomer such as 2-hydroxyethyl acrylate during the production of the (meth) acrylic polymer, a polyisocyanate compound is used. Thus, it is preferable to form a crosslinked structure.

架橋剤の添加量は、(メタ)アクリル系ポリマー100重量部に対して、0.01〜5重量部であることが好ましく、より好ましくは0.02〜2重量部である。架橋剤の添加量が、0.01重量%未満の場合には架橋構造が十分に形成されないため耐久性に劣る傾向にあり、5重量%を超える場合には応力緩和性に劣る傾向がある。   The addition amount of the crosslinking agent is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 2 parts by weight, with respect to 100 parts by weight of the (meth) acrylic polymer. When the addition amount of the crosslinking agent is less than 0.01% by weight, the crosslinked structure is not sufficiently formed, so that the durability tends to be inferior, and when it exceeds 5% by weight, the stress relaxation property tends to be inferior.

本発明の光学部材用粘着剤組成物は、必要に応じて、重合開始剤、紫外線吸収剤、老化防止剤、軟化剤、染料、顔料、充填剤などを配合することができる。   The pressure-sensitive adhesive composition for optical members of the present invention can contain a polymerization initiator, an ultraviolet absorber, an anti-aging agent, a softening agent, a dye, a pigment, a filler, and the like, if necessary.

本発明の粘着型光学部材は、光学部材の片面または両面に、前記光学部材用粘着剤組成物により粘着剤層を形成することにより得られる。   The pressure-sensitive adhesive optical member of the present invention is obtained by forming a pressure-sensitive adhesive layer on one side or both sides of the optical member with the pressure-sensitive adhesive composition for optical members.

光学部材への粘着剤層の形成方法は特に制限されず、1)粘着剤組成物を剥離処理した支持体(剥離シート)に塗布し、乾燥(必要ならば架橋反応)して粘着剤層を形成し、これを光学部材に転写する方法、2)光学部材に直接粘着剤組成物を塗布し、乾燥(必要ならば架橋反応)して粘着剤層を形成する方法等があげられる。   The method for forming the pressure-sensitive adhesive layer on the optical member is not particularly limited. 1) The pressure-sensitive adhesive composition is coated on a release-treated support (release sheet) and dried (if necessary, a crosslinking reaction) to form a pressure-sensitive adhesive layer. And a method of forming the pressure-sensitive adhesive layer by applying the pressure-sensitive adhesive composition directly to the optical member and drying (crosslinking reaction if necessary).

粘着剤組成物の塗布方法としては、リバースコーターやグラビアコーターなどのロールコーター、カーテンコーターやリップコーター、ダイコーターなど任意の塗布方法を採用できる。通常、塗膜の厚さは2〜500μm、好ましくは5〜100μmである。   As an application method of the pressure-sensitive adhesive composition, any application method such as a roll coater such as a reverse coater or a gravure coater, a curtain coater, a lip coater, or a die coater can be adopted. Usually, the thickness of a coating film is 2-500 micrometers, Preferably it is 5-100 micrometers.

支持体(剥離シート)の材料としては、紙、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート等の合成樹脂フィルム、ゴムシート、紙、布、不織布、ネット、発泡シートや金属箔、それらのラミネート体等の適宜な薄葉体等があげられる。支持体の表面には、粘着剤層からの剥離性を高めるため、必要に応じてシリコーン処理、長鎖アルキル処理、フッ素処理な剥離処理が施されていてもよい。   As a material for the support (release sheet), suitable materials such as paper, synthetic resin films such as polyethylene, polypropylene, polyethylene terephthalate, rubber sheets, paper, cloth, nonwoven fabric, nets, foam sheets, metal foils, laminates thereof, and the like Examples include thin leaves. The surface of the support may be subjected to a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment as necessary in order to enhance the peelability from the pressure-sensitive adhesive layer.

粘着型光学部材の表面に粘着剤層が露出する場合は実用に供されるまで剥離処理したシートで保護することが好ましい。   When the pressure-sensitive adhesive layer is exposed on the surface of the pressure-sensitive adhesive optical member, it is preferably protected with a release-treated sheet until it is put to practical use.

光学部材としては液晶表示装置等の形成に用いられるものが使用され、その種類は特に制限されない。たとえば、光学部材としては偏光板があげられる。偏光板は偏光子の片面または両面には透明保護フィルムを有するものが一般に用いられる。   An optical member used for forming a liquid crystal display device or the like is used, and the type thereof is not particularly limited. For example, the optical member includes a polarizing plate. A polarizing plate having a transparent protective film on one or both sides of a polarizer is generally used.

偏光子は、特に制限されず、各種のものを使用できる。偏光子としては、たとえば、ポリビニルアルコール系フィルム、部分ホルマール化ポリビニルアルコール系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料等の二色性物質を吸着させて一軸延伸したもの、ポリビニルアルコールの脱水処理物やポリ塩化ビニルの脱塩酸処理物等ポリエン系配向フィルム等があげられる。これらのなかでもポリビニルアルコール系フィルムとヨウ素などの二色性物質からなる偏光子が好適である。これら偏光子の厚さは特に制限されないが、一般的に、5〜80μm程度である。   The polarizer is not particularly limited, and various types can be used. Examples of the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film, and two colors such as iodine and dichroic dye. Examples thereof include polyene-based oriented films such as those obtained by adsorbing volatile substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 μm.

ポリビニルアルコール系フィルムをヨウ素で染色し一軸延伸した偏光子は、たとえば、ポリビニルアルコールをヨウ素の水溶液に浸漬することによって染色し、元長の3〜7倍に延伸することで作製することができる。必要に応じてホウ酸や硫酸亜鉛、塩化亜鉛等を含んでいてもよいヨウ化カリウムなどの水溶液に浸漬することもできる。さらに必要に応じて染色の前にポリビニルアルコール系フィルムを水に浸漬して水洗してもよい。ポリビニルアルコール系フィルムを水洗することでポリビニルアルコール系フィルム表面の汚れやブロッキング防止剤を洗浄することができるほかに、ポリビニルアルコール系フィルムを膨潤させることで染色のムラなどの不均一を防止する効果もある。延伸はヨウ素で染色した後に行っても良いし、染色しながら延伸してもよいし、また延伸してからヨウ素で染色してもよい。ホウ酸やヨウ化カリウムなどの水溶液中や水浴中でも延伸することができる。   A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous solution of iodine and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride and the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. is there. Stretching may be performed after dyeing with iodine, or may be performed while dyeing, or may be performed with dyeing after iodine. The film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.

前記偏光子の片面または両面に設けられる透明保護フィルムを形成する材料としては、透明性、機械的強度、熱安定性、水分遮蔽性、等方性などに優れるものが好ましい。例えば、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステル系ポリマー、ジアセチルセルロースやトリアセチルセルロース等のセルロース系ポリマー、ポリメチルメタクリレート等のアクリル系ポリマー、ポリスチレンやアクリロニトリル・スチレン共重合体(AS樹脂)等のスチレン系ポリマー、ポリカーボネート系ポリマーなどがあげられる。また、ポリエチレン、ポリプロピレン、シクロ系ないしはノルボルネン構造を有するポリオレフィン、エチレン・プロピレン共重合体の如きポリオレフィン系ポリマー、塩化ビニル系ポリマー、ナイロンや芳香族ポリアミド等のアミド系ポリマー、イミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、ビニルアルコール系ポリマー、塩化ビニリデン系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマー、または前記ポリマーのブレンド物なども前記透明保護フィルムを形成するポリマーの例としてあげられる。透明保護フィルムは、アクリル系、ウレタン系、アクリルウレタン系、エポキシ系、シリコーン系等の熱硬化型、紫外線硬化型の樹脂の硬化層として形成することもできる。   As a material for forming the transparent protective film provided on one side or both sides of the polarizer, a material excellent in transparency, mechanical strength, thermal stability, moisture shielding property, isotropy and the like is preferable. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) -Based polymer, polycarbonate-based polymer and the like. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or the above Polymer blends and the like are also examples of polymers that form the transparent protective film. The transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone.

また、特開2001−343529号公報(WO01/37007)に記載のポリマーフィルム、たとえば、(A)側鎖に置換および/または非置換イミド基を有する熱可塑性樹脂と、(B)側鎖に置換および/非置換フェニルならびにニトリル基を有する熱可塑性樹脂を含有する樹脂組成物があげられる。具体例としてはイソブチレンとN−メチルマレイミドからなる交互共重合体とアクリロニトリル・スチレン共重合体とを含有する樹脂組成物のフィルムがあげられる。フィルムは樹脂組成物の混合押出品などからなるフィルムを用いることができる。   Moreover, the polymer film described in JP-A-2001-343529 (WO01 / 37007), for example, (A) a thermoplastic resin having a substituted and / or unsubstituted imide group in the side chain, and (B) a substitution in the side chain And / or a resin composition containing an unsubstituted phenyl and a thermoplastic resin having a nitrile group. A specific example is a film of a resin composition containing an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile / styrene copolymer. As the film, a film made of a mixed extruded product of the resin composition or the like can be used.

保護フィルムの厚さは、適宜に決定しうるが、一般には強度や取扱性等の作業性、薄層性などの点より1〜500μm程度である。特に1〜300μmが好ましく、5〜200μmがより好ましい。   Although the thickness of a protective film can be determined suitably, generally it is about 1-500 micrometers from points, such as workability | operativity, such as intensity | strength and handleability, and thin layer property. 1-300 micrometers is especially preferable, and 5-200 micrometers is more preferable.

また、保護フィルムは、できるだけ色付きがないことが好ましい。したがって、Rth=(nx−nz)・d(ただし、nxはフィルム平面内の遅相軸方向の屈折率、nzはフィルム厚方向の屈折率、dはフィルム厚みである)で表されるフィルム厚み方向の位相差値が−90nm〜+75nmである保護フィルムが好ましく用いられる。かかる厚み方向の位相差値(Rth)が−90nm〜+75nmのものを使用することにより、保護フィルムに起因する偏光板の着色(光学的な着色)をほぼ解消することができる。厚み方向位相差値(Rth)は、さらに好ましくは−80nm〜+60nm、特に−70nm〜+45nmが好ましい。   Moreover, it is preferable that a protective film has as little color as possible. Therefore, Rth = (nx−nz) · d (where nx is the refractive index in the slow axis direction in the film plane, nz is the refractive index in the film thickness direction, and d is the film thickness). A protective film having a direction retardation value of −90 nm to +75 nm is preferably used. By using a film having a thickness direction retardation value (Rth) of −90 nm to +75 nm, the coloring (optical coloring) of the polarizing plate caused by the protective film can be almost eliminated. The thickness direction retardation value (Rth) is more preferably −80 nm to +60 nm, and particularly preferably −70 nm to +45 nm.

保護フィルムとしては、偏光特性や耐久性などの点より、トリアセチルセルロース等のセルロース系ポリマーが好ましい。特にトリアセチルセルロースフィルムが好適である。なお、偏光子の両側に保護フィルムを設ける場合、その表裏で同じポリマー材料からなる保護フィルムを用いてもよく、異なるポリマー材料等からなる保護フィルムを用いてもよい。前記偏光子と保護フィルムとは通常、水系粘着剤等を介して密着している。水系接着剤としては、イソシアネート系接着剤、ポリビニルアルコール系接着剤、ゼラチン系接着剤、ビニル系ラテックス系、水系ポリウレタン、水系ポリエステル等を例示できる。   As the protective film, a cellulose polymer such as triacetyl cellulose is preferable from the viewpoints of polarization characteristics and durability. A triacetyl cellulose film is particularly preferable. In addition, when providing a protective film in the both sides of a polarizer, the protective film which consists of the same polymer material may be used by the front and back, and the protective film which consists of a different polymer material etc. may be used. The polarizer and the protective film are usually in close contact with each other through an aqueous adhesive or the like. Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester.

前記透明保護フィルムの偏光子を接着させない面には、ハードコート層や反射防止処理、スティッキング防止や、拡散ないしアンチグレアを目的とした処理を施したものであってもよい。   The surface of the transparent protective film to which the polarizer is not adhered may be subjected to a hard coat layer, an antireflection treatment, an antisticking treatment, or a treatment for diffusion or antiglare.

ハードコート処理は偏光板表面の傷付き防止などを目的に施されるものであり、例えばアクリル系、シリコーン系などの適宜な紫外線硬化型樹脂による硬度や滑り特性等に優れる硬化皮膜を透明保護フィルムの表面に付加する方式などにて形成することができる。反射防止処理は偏光板表面での外光の反射防止を目的に施されるものであり、従来に準じた反射防止膜などの形成により達成することができる。また、スティッキング防止処理は隣接層との密着防止を目的に施される。   The hard coat treatment is applied for the purpose of preventing scratches on the surface of the polarizing plate. For example, a transparent protective film with a cured film excellent in hardness, sliding properties, etc. by an appropriate ultraviolet curable resin such as acrylic or silicone is used. It can be formed by a method of adding to the surface of the film. The antireflection treatment is performed for the purpose of preventing reflection of external light on the surface of the polarizing plate, and can be achieved by forming an antireflection film or the like according to the conventional art. Further, the anti-sticking treatment is performed for the purpose of preventing adhesion with an adjacent layer.

またアンチグレア処理は偏光板の表面で外光が反射して偏光板透過光の視認を阻害することの防止等を目的に施されるものであり、例えばサンドブラスト方式やエンボス加工方式による粗面化方式や透明微粒子の配合方式などの適宜な方式にて透明保護フィルムの表面に微細凹凸構造を付与することにより形成することができる。前記表面微細凹凸構造の形成に含有させる微粒子としては、例えば平均粒子径が0.5〜50μmのシリカ、アルミナ、チタニア、ジルコニア、酸化錫、酸化インジウム、酸化カドミウム、酸化アンチモン等からなる導電性のこともある無機系微粒子、架橋又は未架橋のポリマー等からなる有機系微粒子などの透明微粒子が用いられる。表面微細凹凸構造を形成する場合、微粒子の使用量は、表面微細凹凸構造を形成する透明樹脂100重量部に対して一般的に2〜50重量部程度であり、5〜25重量部が好ましい。アンチグレア層は、偏光板透過光を拡散して視角などを拡大するための拡散層(視角拡大機能など)を兼ねるものであってもよい。   The anti-glare treatment is applied for the purpose of preventing the outside light from being reflected on the surface of the polarizing plate and obstructing the visibility of the light transmitted through the polarizing plate. For example, the surface is roughened by a sandblasting method or an embossing method. It can be formed by imparting a fine concavo-convex structure to the surface of the transparent protective film by an appropriate method such as a blending method of transparent fine particles. The fine particles to be included in the formation of the surface fine concavo-convex structure are, for example, conductive materials made of silica, alumina, titania, zirconia, tin oxide, indium oxide, cadmium oxide, antimony oxide or the like having an average particle diameter of 0.5 to 50 μm. In some cases, transparent fine particles such as inorganic fine particles, organic fine particles composed of a crosslinked or uncrosslinked polymer, and the like are used. When forming a surface fine uneven structure, the amount of fine particles used is generally about 2 to 50 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the transparent resin forming the surface fine uneven structure. The antiglare layer may also serve as a diffusion layer (viewing angle expanding function or the like) for diffusing the light transmitted through the polarizing plate to expand the viewing angle.

なお、前記反射防止層、スティッキング防止層、拡散層やアンチグレア層等は、透明保護フィルムそのものに設けることができるほか、別途光学層として透明保護フィルムとは別体のものとして設けることもできる。   The antireflection layer, antisticking layer, diffusion layer, antiglare layer, and the like can be provided on the transparent protective film itself, or can be provided separately from the transparent protective film as an optical layer.

また本発明の光学部材としては、例えば反射板や半透過板、位相差板(1/2 や1/4等の波長板を含む)、視角補償フィルム、輝度向上フィルムなどの液晶表示装置等の形成に用いられることのある光学層となるものがあげられる。これらは単独で本発明の光学部材として用いることができる他、前記偏光板に、実用に際して積層して、1層または2層以上用いることができる。   The optical member of the present invention includes, for example, a liquid crystal display device such as a reflecting plate, a transflective plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), a viewing angle compensation film, and a brightness enhancement film. What becomes an optical layer which may be used for formation is mention | raise | lifted. These can be used alone as the optical member of the present invention, and can be laminated on the polarizing plate for practical use and used in one or more layers.

特に、偏光板に更に反射板または半透過反射板が積層されてなる反射型偏光板または半透過型偏光板、偏光板に更に位相差板が積層されてなる楕円偏光板または円偏光板、偏光板に更に視角補償フィルムが積層されてなる広視野角偏光板、あるいは偏光板に更に輝度向上フィルムが積層されてなる偏光板が好ましい。   In particular, a reflective polarizing plate or a semi-transmissive polarizing plate in which a polarizing plate is further laminated with a reflecting plate or a semi-transmissive reflecting plate, an elliptical polarizing plate or a circular polarizing plate in which a retardation plate is further laminated on a polarizing plate, a polarizing plate A wide viewing angle polarizing plate in which a viewing angle compensation film is further laminated on a plate, or a polarizing plate in which a brightness enhancement film is further laminated on a polarizing plate is preferable.

反射型偏光板は、偏光板に反射層を設けたもので、視認側(表示側)からの入射光を反射させて表示するタイプの液晶表示装置などを形成するためのものであり、バックライト等の光源の内蔵を省略できて液晶表示装置の薄型化を図りやすいなどの利点を有する。反射型偏光板の形成は、必要に応じ透明保護層等を介して偏光板の片面に金属等からなる反射層を付設する方式などの適宜な方式にて行うことができる。   A reflective polarizing plate is a polarizing plate provided with a reflective layer, and is used to form a liquid crystal display device or the like that reflects incident light from the viewing side (display side). Such a light source can be omitted, and the liquid crystal display device can be easily thinned. The reflective polarizing plate can be formed by an appropriate method such as a method in which a reflective layer made of metal or the like is attached to one surface of the polarizing plate via a transparent protective layer or the like as necessary.

反射型偏光板の具体例としては、必要に応じマット処理した透明保護フィルムの片面に、アルミニウム等の反射性金属からなる箔や蒸着膜を付設して反射層を形成したものなどがあげられる。また前記透明保護フィルムに微粒子を含有させて表面微細凹凸構造とし、その上に微細凹凸構造の反射層を有するものなどもあげられる。前記した微細凹凸構造の反射層は、入射光を乱反射により拡散させて指向性やギラギラした見栄えを防止し、明暗のムラを抑制しうる利点などを有する。また微粒子含有の透明保護フィルムは、入射光及びその反射光がそれを透過する際に拡散されて明暗ムラをより抑制しうる利点なども有している。透明保護フィルムの表面微細凹凸構造を反映させた微細凹凸構造の反射層の形成は、例えば真空蒸着方式、イオンプレーティング方式、スパッタリング方式等の蒸着方式やメッキ方式などの適宜な方式で金属を透明保護層の表面に直接付設する方法などにより行うことができる。   Specific examples of the reflective polarizing plate include those in which a reflective layer is formed by attaching a foil or a vapor deposition film made of a reflective metal such as aluminum on one side of a transparent protective film matted as necessary. Moreover, the transparent protective film contains fine particles so as to have a surface fine concavo-convex structure and a reflective layer having a fine concavo-convex structure thereon. The reflective layer having the fine concavo-convex structure has an advantage that incident light is diffused by irregular reflection to prevent directivity and glaring appearance and to suppress unevenness in brightness and darkness. The transparent protective film containing fine particles also has an advantage that incident light and its reflected light are diffused when passing through it, and light and dark unevenness can be further suppressed. The reflective layer of the fine concavo-convex structure reflecting the surface fine concavo-convex structure of the transparent protective film is formed by transparent the metal by an appropriate method such as a vapor deposition method such as a vacuum vapor deposition method, an ion plating method, a sputtering method, or a plating method. It can be performed by a method of directly attaching to the surface of the protective layer.

反射板は前記の偏光板の透明保護フィルムに直接付与する方式に代えて、その透明フィルムに準じた適宜なフィルムに反射層を設けてなる反射シートなどとして用いることもできる。なお反射層は、通常、金属からなるので、その反射面が透明保護フィルムや偏光板等で被覆された状態の使用形態が、酸化による反射率の低下防止、ひいては初期反射率の長期持続の点や、保護層の別途付設の回避の点などより好ましい。   Instead of the method of directly applying the reflecting plate to the transparent protective film of the polarizing plate, the reflecting plate can be used as a reflecting sheet provided with a reflecting layer on an appropriate film according to the transparent film. Since the reflective layer is usually made of metal, the usage form in which the reflective surface is covered with a transparent protective film, a polarizing plate or the like is used to prevent the reflectance from being lowered due to oxidation, and thus to maintain the initial reflectance for a long time. In addition, it is more preferable to avoid a separate attachment of the protective layer.

なお、半透過型偏光板は、上記において反射層で光を反射し、かつ透過するハーフミラー等の半透過型の反射層とすることにより得ることができる。半透過型偏光板は、通常液晶セルの裏側に設けられ、液晶表示装置などを比較的明るい雰囲気で使用する場合には、視認側(表示側)からの入射光を反射させて画像を表示し、比較的暗い雰囲気においては、半透過型偏光板のバックサイドに内蔵されているバックライト等の内蔵光源を使用して画像を表示するタイプの液晶表示装置などを形成できる。すなわち、半透過型偏光板は、明るい雰囲気下では、バックライト等の光源使用のエネルギーを節約でき、比較的暗い雰囲気下においても内蔵光源を用いて使用できるタイプの液晶表示装置などの形成に有用である。   The semi-transmissive polarizing plate can be obtained by using a semi-transmissive reflective layer such as a half mirror that reflects and transmits light with the reflective layer. A transflective polarizing plate is usually provided on the back side of a liquid crystal cell, and displays an image by reflecting incident light from the viewing side (display side) when a liquid crystal display device is used in a relatively bright atmosphere. In a relatively dark atmosphere, a liquid crystal display device or the like that displays an image using a built-in light source such as a backlight built in the back side of the transflective polarizing plate can be formed. In other words, the transflective polarizing plate is useful for forming a liquid crystal display device of a type that can save energy of using a light source such as a backlight in a bright atmosphere and can be used with a built-in light source even in a relatively dark atmosphere. It is.

偏光板に更に位相差板が積層されてなる楕円偏光板または円偏光板について説明する。直線偏光を楕円偏光または円偏光に変えたり、楕円偏光または円偏光を直線偏光に変えたり、あるいは直線偏光の偏光方向を変える場合に、位相差板などが用いられる。特に、直線偏光を円偏光に変えたり、円偏光を直線偏光に変える位相差板としては、いわゆる1/4波長板(λ/4板とも言う)が用いられる。1/2波長板(λ/2板とも言う)は、通常、直線偏光の偏光方向を変える場合に用いられる。   An elliptically polarizing plate or a circularly polarizing plate in which a retardation plate is further laminated on a polarizing plate will be described. A phase difference plate or the like is used when changing linearly polarized light to elliptically polarized light or circularly polarized light, changing elliptically polarized light or circularly polarized light to linearly polarized light, or changing the polarization direction of linearly polarized light. In particular, a so-called quarter-wave plate (also referred to as a λ / 4 plate) is used as a retardation plate that changes linearly polarized light into circularly polarized light or changes circularly polarized light into linearly polarized light. A half-wave plate (also referred to as a λ / 2 plate) is usually used when changing the polarization direction of linearly polarized light.

楕円偏光板はスーパーツイストネマチック(STN)型液晶表示装置の液晶層の複屈折により生じた着色(青又は黄)を補償(防止)して、前記着色のない白黒表示する場合などに有効に用いられる。更に、三次元の屈折率を制御したものは、液晶表示装置の画面を斜め方向から見た際に生じる着色も補償(防止)することができて好ましい。円偏光板は、例えば画像がカラー表示になる反射型液晶表示装置の画像の色調を整える場合などに有効に用いられ、また、反射防止の機能も有する。   The elliptically polarizing plate is effectively used for black and white display without the above color by compensating (preventing) the coloration (blue or yellow) generated by the birefringence of the liquid crystal layer of the super twist nematic (STN) type liquid crystal display device. It is done. Further, the one in which the three-dimensional refractive index is controlled is preferable because it can compensate (prevent) coloring that occurs when the screen of the liquid crystal display device is viewed from an oblique direction. The circularly polarizing plate is effectively used, for example, when adjusting the color tone of an image of a reflective liquid crystal display device in which an image is displayed in color, and also has an antireflection function.

位相差板としては、高分子素材を一軸または二軸延伸処理してなる複屈折性フィルム、液晶ポリマーの配向フィルム、液晶ポリマーの配向層をフィルムにて支持したものなどがあげられる。位相差板の厚さも特に制限されないが、20〜150μm程度が一般的である。   Examples of the retardation plate include a birefringent film obtained by uniaxially or biaxially stretching a polymer material, a liquid crystal polymer alignment film, and a liquid crystal polymer alignment layer supported by a film. The thickness of the retardation plate is not particularly limited, but is generally about 20 to 150 μm.

高分子素材としては、たとえば、ポリビニルアルコール、ポリビニルブチラール、ポリメチルビニルエーテル、ポリヒドロキシエチルアクリレート、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、メチルセルロース、ポリカーボネート、ポリアリレート、ポリスルホン、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリエーテルスルホン、ポリフェニレンスルファイド、ポリフェニレンオキサイド、ポリアリルスルホン、ポリビニルアルコール、ポリアミド、ポリイミド、ポリオレフィン、ポリ塩化ビニル、セルロース系重合体、ノルボルネン系樹脂、またはこれらの二元系、三元系各種共重合体、グラフト共重合体、ブレンド物などがあげられる。これら高分子素材は延伸等により配向物(延伸フィルム)となる。   Examples of the polymer material include polyvinyl alcohol, polyvinyl butyral, polymethyl vinyl ether, polyhydroxyethyl acrylate, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, polycarbonate, polyarylate, polysulfone, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, Polyphenylene sulfide, polyphenylene oxide, polyallylsulfone, polyvinyl alcohol, polyamide, polyimide, polyolefin, polyvinyl chloride, cellulose polymer, norbornene resin, or binary, ternary various copolymers, graft copolymers Examples thereof include polymers and blends. These polymer materials become oriented products (stretched films) by stretching or the like.

液晶性ポリマーとしては、たとえば、液晶配向性を付与する共役性の直線状原子団(メソゲン)がポリマーの主鎖や側鎖に導入された主鎖型や側鎖型の各種のものなどがあげられる。主鎖型の液晶性ポリマーの具体例としては、屈曲性を付与するスペーサ部でメソゲン基を結合した構造の、例えばネマチック配向性のポリエステル系液晶性ポリマー、ディスコティックポリマーやコレステリックポリマーなどがあげられる。側鎖型の液晶性ポリマーの具体例としては、ポリシロキサン、ポリアクリレート、ポリメタクリレート又はポリマロネートを主鎖骨格とし、側鎖として共役性の原子団からなるスペーサ部を介してネマチック配向付与性のパラ置換環状化合物単位からなるメソゲン部を有するものなどがあげられる。これら液晶性ポリマーは、たとえば、ガラス板上に形成したポリイミドやポリビニルアルコール等の薄膜の表面をラビング処理したもの、酸化珪素を斜方蒸着したものなどの配向処理面上に液晶性ポリマーの溶液を展開して熱処理することにより行われる。   Examples of the liquid crystalline polymer include various main chain types and side chain types in which a conjugated linear atomic group (mesogen) imparting liquid crystal alignment is introduced into the main chain or side chain of the polymer. It is done. Specific examples of the main chain type liquid crystalline polymer include, for example, a nematic alignment polyester liquid crystalline polymer, a discotic polymer, and a cholesteric polymer having a structure in which a mesogen group is bonded to a spacer portion that imparts flexibility. . Specific examples of the side chain type liquid crystalline polymer include polysiloxane, polyacrylate, polymethacrylate, or polymalonate as a main chain skeleton, and a nematic alignment imparting paraffin through a spacer portion composed of a conjugated atomic group as a side chain. Examples thereof include those having a mesogen moiety composed of a substituted cyclic compound unit. These liquid crystalline polymers are prepared by, for example, applying a solution of a liquid crystalline polymer on an alignment surface such as those obtained by rubbing the surface of a thin film such as polyimide or polyvinyl alcohol formed on a glass plate, or by obliquely depositing silicon oxide. This is done by developing and heat treatment.

位相差板は、例えば各種波長板や液晶層の複屈折による着色や視角等の補償を目的としたものなどの使用目的に応じた適宜な位相差を有するものであってよく、2種以上の位相差板を積層して位相差等の光学特性を制御したものなどであってもよい。   The retardation plate may have an appropriate retardation according to the purpose of use, such as those for the purpose of compensating for various wavelength plates or birefringence of the liquid crystal layer, viewing angle, and the like. What laminated | stacked the phase difference plate and controlled optical characteristics, such as phase difference, etc. may be used.

また上記の楕円偏光板や反射型楕円偏光板は、偏光板又は反射型偏光板と位相差板を適宜な組合せで積層したものである。かかる楕円偏光板等は、(反射型)偏光板と位相差板の組合せとなるようにそれらを液晶表示装置の製造過程で順次別個に積層することによっても形成しうるが、前記の如く予め楕円偏光板等の光学部材としたものは、品質の安定性や積層作業性等に優れて液晶表示装置などの製造効率を向上させうる利点がある。   The elliptical polarizing plate and the reflective elliptical polarizing plate are obtained by laminating a polarizing plate or a reflective polarizing plate and a retardation plate in an appropriate combination. Such an elliptically polarizing plate or the like can also be formed by sequentially laminating them sequentially in the manufacturing process of the liquid crystal display device so as to be a combination of a (reflective) polarizing plate and a retardation plate. An optical member such as a polarizing plate has an advantage that it can improve the production efficiency of a liquid crystal display device and the like because of excellent quality stability and lamination workability.

視角補償フィルムは、液晶表示装置の画面を、画面に垂直でなくやや斜めの方向から見た場合でも、画像が比較的鮮明にみえるように視野角を広げるためのフィルムである。このような視角補償位相差板としては、例えば位相差板、液晶ポリマー等の配向フィルムや透明基材上に液晶ポリマー等の配向層を支持したものなどからなる。通常の位相差板は、その面方向に一軸に延伸された複屈折を有するポリマーフィルムが用いられるのに対し、視角補償フィルムとして用いられる位相差板には、面方向に二軸に延伸された複屈折を有するポリマーフィルムとか、面方向に一軸に延伸され厚さ方向にも延伸された厚さ方向の屈折率を制御した複屈折を有するポリマーや傾斜配向フィルムのような二方向延伸フィルムなどが用いられる。傾斜配向フィルムとしては、例えばポリマーフィルムに熱収縮フィルムを接着して加熱によるその収縮力の作用下にポリマーフィルムを延伸処理又は/及び収縮処理したものや、液晶ポリマーを斜め配向させたものなどが挙げられる。位相差板の素材原料ポリマーは、先の位相差板で説明したポリマーと同様のものが用いられ、液晶セルによる位相差に基づく視認角の変化による着色等の防止や良視認の視野角の拡大などを目的とした適宜なものを用いうる。   The viewing angle compensation film is a film for widening the viewing angle so that an image can be seen relatively clearly even when the screen of the liquid crystal display device is viewed from a slightly oblique direction rather than perpendicular to the screen. As such a viewing angle compensation phase difference plate, for example, a phase difference plate, an alignment film such as a liquid crystal polymer, or an alignment layer such as a liquid crystal polymer supported on a transparent substrate is used. A normal retardation plate uses a birefringent polymer film uniaxially stretched in the plane direction, whereas a retardation plate used as a viewing angle compensation film stretches biaxially in the plane direction. Birefringent polymer film, biaxially stretched film such as polymer with birefringence with a controlled refractive index in the thickness direction that is uniaxially stretched in the plane direction and stretched in the thickness direction, etc. Used. Examples of the inclined alignment film include a film obtained by bonding a heat shrink film to a polymer film and stretching or / and shrinking the polymer film under the action of the contraction force by heating, and a film obtained by obliquely aligning a liquid crystal polymer. Can be mentioned. The raw material polymer for the phase difference plate is the same as the polymer described in the previous phase difference plate, preventing coloration due to a change in the viewing angle based on the phase difference by the liquid crystal cell and expanding the viewing angle for good visual recognition. An appropriate one for the purpose can be used.

また良視認の広い視野角を達成する点などより、液晶ポリマーの配向層、特にディスコティック液晶ポリマーの傾斜配向層からなる光学的異方性層をトリアセチルセルロースフィルムにて支持した光学補償位相差板が好ましく用いうる。   Also, from the viewpoint of achieving a wide viewing angle with good visibility, an optically compensated phase difference in which a liquid crystal polymer alignment layer, in particular an optically anisotropic layer composed of a discotic liquid crystal polymer gradient alignment layer, is supported by a triacetylcellulose film. A plate can be preferably used.

偏光板と輝度向上フィルムを貼り合わせた偏光板は、通常液晶セルの裏側サイドに設けられて使用される。輝度向上フィルムは、液晶表示装置などのバックライトや裏側からの反射などにより自然光が入射すると所定偏光軸の直線偏光または所定方向の円偏光を反射し、他の光は透過する特性を示すもので、輝度向上フィルムを偏光板と積層した偏光板は、バックライト等の光源からの光を入射させて所定偏光状態の透過光を得ると共に、前記所定偏光状態以外の光は透過せずに反射される。この輝度向上フィルム面で反射した光を更にその後ろ側に設けられた反射層等を介し反転させて輝度向上フィルムに再入射させ、その一部又は全部を所定偏光状態の光として透過させて輝度向上フィルムを透過する光の増量を図ると共に、偏光子に吸収させにくい偏光を供給して液晶表示画像表示等に利用しうる光量の増大を図ることにより輝度を向上させうるものである。すなわち、輝度向上フィルムを使用せずに、バックライトなどで液晶セルの裏側から偏光子を通して光を入射した場合には、偏光子の偏光軸に一致していない偏光方向を有する光は、ほとんど偏光子に吸収されてしまい、偏光子を透過してこない。すなわち、用いた偏光子の特性によっても異なるが、およそ50%の光が偏光子に吸収されてしまい、その分、液晶画像表示等に利用しうる光量が減少し、画像が暗くなる。輝度向上フィルムは、偏光子に吸収されるような偏光方向を有する光を偏光子に入射させずに輝度向上フィルムで一旦反射させ、更にその後ろ側に設けられた反射層等を介して反転させて輝度向上フィルムに再入射させることを繰り返し、この両者間で反射、反転している光の偏光方向が偏光子を通過し得るような偏光方向になった偏光のみを、輝度向上フィルムは透過させて偏光子に供給するので、バックライトなどの光を効率的に液晶表示装置の画像の表示に使用でき、画面を明るくすることができる。   A polarizing plate obtained by bonding a polarizing plate and a brightness enhancement film is usually provided on the back side of a liquid crystal cell. The brightness enhancement film reflects a linearly polarized light with a predetermined polarization axis or a circularly polarized light in a predetermined direction when natural light is incident due to a backlight such as a liquid crystal display device or reflection from the back side, and transmits other light. In addition, a polarizing plate in which a brightness enhancement film is laminated with a polarizing plate allows light from a light source such as a backlight to enter to obtain transmitted light in a predetermined polarization state, and reflects light without transmitting the light other than the predetermined polarization state. The The light reflected on the surface of the brightness enhancement film is further inverted through a reflective layer or the like provided behind the brightness enhancement film and re-incident on the brightness enhancement film, and part or all of the light is transmitted as light having a predetermined polarization state. Luminance can be improved by increasing the amount of light transmitted through the enhancement film and increasing the amount of light that can be used for liquid crystal display image display or the like by supplying polarized light that is difficult to be absorbed by the polarizer. That is, when light is incident through the polarizer from the back side of the liquid crystal cell without using a brightness enhancement film, light having a polarization direction that does not coincide with the polarization axis of the polarizer is almost polarized. It is absorbed by the polarizer and does not pass through the polarizer. That is, although depending on the characteristics of the polarizer used, approximately 50% of the light is absorbed by the polarizer, and the amount of light that can be used for liquid crystal image display or the like is reduced accordingly, resulting in a dark image. The brightness enhancement film allows light having a polarization direction that is absorbed by the polarizer to be reflected once by the brightness enhancement film without being incident on the polarizer, and further inverted through a reflective layer provided on the rear side thereof. Repeatedly re-enter the brightness enhancement film, and the brightness enhancement film transmits only polarized light whose polarization direction is such that the polarization direction of light reflected and inverted between the two can pass through the polarizer. Therefore, light such as a backlight can be efficiently used for displaying an image on the liquid crystal display device, and the screen can be brightened.

輝度向上フィルムと上記反射層等の間に拡散板を設けることもできる。輝度向上フィルムによって反射した偏光状態の光は上記反射層等に向かうが、設置された拡散板は通過する光を均一に拡散すると同時に偏光状態を解消し、非偏光状態となる。すなわち、拡散板は偏光を元の自然光状態にもどす。この非偏光状態、すなわち自然光状態の光が反射層等に向かい、反射層等を介して反射し、再び拡散板を通過して輝度向上フィルムに再入射することを繰り返す。このように輝度向上フィルムと上記反射層等の間に、偏光を元の自然光状態にもどす拡散板を設けることにより表示画面の明るさを維持しつつ、同時に表示画面の明るさのむらを少なくし、均一で明るい画面を提供することができる。かかる拡散板を設けることにより、初回の入射光は反射の繰り返し回数が程よく増加し、拡散板の拡散機能と相俟って均一の明るい表示画面を提供することができたものと考えられる。   A diffusion plate may be provided between the brightness enhancement film and the reflective layer. The polarized light reflected by the brightness enhancement film is directed to the reflective layer or the like, but the installed diffuser plate uniformly diffuses the light passing therethrough and simultaneously cancels the polarized state and becomes a non-polarized state. That is, the diffuser plate returns the polarized light to the original natural light state. The light in the non-polarized state, that is, the natural light state is directed toward the reflection layer and the like, reflected through the reflection layer and the like, and again passes through the diffusion plate and reenters the brightness enhancement film. Thus, while maintaining the brightness of the display screen by providing a diffuser plate that returns polarized light to the original natural light state between the brightness enhancement film and the reflective layer, etc., the brightness unevenness of the display screen is reduced at the same time, A uniform and bright screen can be provided. By providing such a diffuser plate, it is considered that the first incident light has a moderate increase in the number of repetitions of reflection, and in combination with the diffusion function of the diffuser plate, a uniform bright display screen can be provided.

前記の輝度向上フィルムとしては、例えば誘電体の多層薄膜や屈折率異方性が相違する薄膜フィルムの多層積層体の如き、所定偏光軸の直線偏光を透過して他の光は反射する特性を示すもの、コレステリック液晶ポリマーの配向フィルムやその配向液晶層をフィルム基材上に支持したものの如き、左回り又は右回りのいずれか一方の円偏光を反射して他の光は透過する特性を示すものなどの適宜なものを用いうる。   The brightness enhancement film has a characteristic of transmitting linearly polarized light having a predetermined polarization axis and reflecting other light, such as a multilayer thin film of dielectric material or a multilayer laminate of thin film films having different refractive index anisotropies. Such as an alignment film of a cholesteric liquid crystal polymer or an alignment liquid crystal layer supported on a film substrate, which reflects either left-handed or right-handed circularly polarized light and transmits other light. Appropriate things, such as a thing, can be used.

従って、前記した所定偏光軸の直線偏光を透過させるタイプの輝度向上フィルムでは、その透過光をそのまま偏光板に偏光軸を揃えて入射させることにより、偏光板による吸収ロスを抑制しつつ効率よく透過させることができる。一方、コレステリック液晶層の如く円偏光を投下するタイプの輝度向上フィルムでは、そのまま偏光子に入射させることもできるが、吸収ロスを抑制する点よりその円偏光を位相差板を介し直線偏光化して偏光板に入射させることが好ましい。なお、その位相差板として1/4波長板を用いることにより、円偏光を直線偏光に変換することができる。   Therefore, in the brightness enhancement film of the type that transmits linearly polarized light having the predetermined polarization axis as described above, the transmitted light is incident on the polarizing plate with the polarization axis aligned as it is, thereby efficiently transmitting while suppressing absorption loss due to the polarizing plate. Can be made. On the other hand, in a brightness enhancement film of a type that emits circularly polarized light such as a cholesteric liquid crystal layer, it can be incident on a polarizer as it is, but from the viewpoint of suppressing absorption loss, the circularly polarized light is linearly polarized through a retardation plate. It is preferable to make it enter into a polarizing plate. Note that circularly polarized light can be converted to linearly polarized light by using a quarter wave plate as the retardation plate.

可視光域等の広い波長範囲で1/4波長板として機能する位相差板は、例えば波長550nmの淡色光に対して1/4波長板として機能する位相差層と他の位相差特性を示す位相差層、例えば1/2波長板として機能する位相差層とを重畳する方式などにより得ることができる。従って、偏光板と輝度向上フィルムの間に配置する位相差板は、1層又は2層以上の位相差層からなるものであってよい。   A retardation plate that functions as a quarter-wave plate in a wide wavelength range such as a visible light region exhibits, for example, a retardation layer that functions as a quarter-wave plate for light-color light having a wavelength of 550 nm and other retardation characteristics. It can be obtained by a method of superposing a retardation layer, for example, a retardation layer functioning as a half-wave plate. Therefore, the retardation plate disposed between the polarizing plate and the brightness enhancement film may be composed of one or more retardation layers.

なお、コレステリック液晶層についても、反射波長が相違するものの組み合わせにして2層又は3層以上重畳した配置構造とすることにより、可視光領域等の広い波長範囲で円偏光を反射するものを得ることができ、それに基づいて広い波長範囲の透過円偏光を得ることができる。   In addition, the cholesteric liquid crystal layer can also be obtained by reflecting circularly polarized light in a wide wavelength range such as a visible light region by combining two or more layers having different reflection wavelengths and having an overlapping structure. Based on this, transmitted circularly polarized light in a wide wavelength range can be obtained.

また、偏光板は、上記の偏光分離型偏光板の如く、偏光板と2層又は3層以上の光学層とを積層したものからなっていてもよい。従って、上記の反射型偏光板や半透過型偏光板と位相差板を組み合わせた反射型楕円偏光板や半透過型楕円偏光板などであってもよい。   Further, the polarizing plate may be formed by laminating a polarizing plate and two or three or more optical layers like the above-described polarization separation type polarizing plate. Therefore, a reflective elliptical polarizing plate or a semi-transmissive elliptical polarizing plate in which the above-mentioned reflective polarizing plate or transflective polarizing plate and a retardation plate are combined may be used.

偏光板に前記光学層を積層した光学部材は、液晶表示装置等の製造過程で順次別個に積層する方式にても形成することができるが、予め積層して光学部材としたのものは、品質の安定性や組立作業等に優れていて液晶表示装置などの製造工程を向上させうる利点がある。積層には粘着層等の適宜な接着手段を用いうる。前記の偏光板と他の光学層の接着に際し、それらの光学軸は目的とする位相差特性などに応じて適宜な配置角度とすることができる。   The optical member in which the optical layer is laminated on the polarizing plate can be formed by a method of sequentially laminating separately in the manufacturing process of a liquid crystal display device or the like. There is an advantage that the manufacturing process of the liquid crystal display device and the like can be improved. For the lamination, an appropriate adhesive means such as an adhesive layer can be used. When adhering the polarizing plate and the other optical layer, their optical axes can be set at an appropriate arrangement angle in accordance with the target phase difference characteristic.

なお、本発明の粘着型光学部材の光学部材や粘着剤層などの各層には、例えばサリチル酸エステル系化合物やべンゾフェノール系化合物、ベンゾトリアゾール系化合物やシアノアクリレート系化合物、ニッケル錯塩系化合物等の紫外線吸収剤で処理する方式などの方式により紫外線吸収能をもたせたものなどであってもよい。   In addition, each layer such as the optical member and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive optical member of the present invention includes, for example, an ultraviolet ray such as a salicylic acid ester compound, a benzophenol compound, a benzotriazole compound, a cyanoacrylate compound, or a nickel complex compound. What gave the ultraviolet absorptivity by systems, such as a system processed with an absorber, may be used.

本発明の粘着型光学部材は液晶表示装置等の各種画像表示装置の形成などに好ましく用いることができる。液晶表示装置の形成は、従来に準じて行いうる。すなわち液晶表示装置は一般に、液晶セルと粘着型光学部材、及び必要に応じての照明システム等の構成部品を適宜に組立てて駆動回路を組込むことなどにより形成されるが、本発明においては本発明による光学部材を用いる点を除いて特に限定はなく、従来に準じうる。液晶セルについても、例えばTN型やSTN型、π型などの任意なタイプのものを用いうる。   The pressure-sensitive adhesive optical member of the present invention can be preferably used for forming various image display devices such as a liquid crystal display device. The liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, an adhesive optical member, and an illumination system as necessary, and incorporating a drive circuit. There is no particular limitation except that an optical member is used. As the liquid crystal cell, any type such as a TN type, an STN type, or a π type can be used.

液晶セルの片側又は両側に粘着型光学部材を配置した液晶表示装置や、照明システムにバックライトあるいは反射板を用いたものなどの適宜な液晶表示装置を形成することができる。その場合、本発明による光学部材は液晶セルの片側又は両側に設置することができる。両側に光学部材を設ける場合、それらは同じものであってもよいし、異なるものであってもよい。さらに、液晶表示装置の形成に際しては、例えば拡散板、アンチグレア層、反射防止膜、保護板、プリズムアレイ、レンズアレイシート、光拡散板、バックライトなどの適宜な部品を適宜な位置に1層又は2層以上配置することができる。   An appropriate liquid crystal display device such as a liquid crystal display device in which an adhesive optical member is disposed on one side or both sides of a liquid crystal cell, or a backlight or a reflector used in an illumination system can be formed. In that case, the optical member by this invention can be installed in the one side or both sides of a liquid crystal cell. When optical members are provided on both sides, they may be the same or different. Further, when forming a liquid crystal display device, for example, a single layer or a suitable part such as a diffusing plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusing plate, a backlight, etc. Two or more layers can be arranged.

次いで有機エレクトロルミネセンス装置(有機EL表示装置)について説明する。一般に、有機EL表示装置は、透明基板上に透明電極と有機発光層と金属電極とを順に積層して発光体(有機エレクトロルミネセンス発光体)を形成している。ここで、有機発光層は、種々の有機薄膜の積層体であり、例えばトリフェニルアミン誘導体等からなる正孔注入層と、アントラセン等の蛍光性の有機固体からなる発光層との積層体や、あるいはこのような発光層とペリレン誘導体等からなる電子注入層の積層体や、またあるいはこれらの正孔注入層、発光層、および電子注入層の積層体等、種々の組み合わせをもった構成が知られている。   Next, an organic electroluminescence device (organic EL display device) will be described. Generally, in an organic EL display device, a transparent electrode, an organic light emitting layer, and a metal electrode are sequentially laminated on a transparent substrate to form a light emitter (organic electroluminescent light emitter). Here, the organic light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative and the like and a light emitting layer made of a fluorescent organic solid such as anthracene, Alternatively, a structure having various combinations such as a laminate of such a light emitting layer and an electron injection layer composed of a perylene derivative or the like, or a laminate of these hole injection layer, light emitting layer, and electron injection layer is known. It has been.

有機EL表示装置は、透明電極と金属電極とに電圧を印加することによって、有機発光層に正孔と電子とが注入され、これら正孔と電子との再結合によって生じるエネルギーが蛍光物資を励起し、励起された蛍光物質が基底状態に戻るときに光を放射する、という原理で発光する。途中の再結合というメカニズムは、一般のダイオードと同様であり、このことからも予想できるように、電流と発光強度は印加電圧に対して整流性を伴う強い非線形性を示す。   In organic EL display devices, holes and electrons are injected into the organic light-emitting layer by applying a voltage to the transparent electrode and the metal electrode, and the energy generated by recombination of these holes and electrons excites the phosphor material. Then, light is emitted on the principle that the excited fluorescent material emits light when returning to the ground state. The mechanism of recombination in the middle is the same as that of a general diode, and as can be predicted from this, the current and the emission intensity show strong nonlinearity with rectification with respect to the applied voltage.

有機EL表示装置においては、有機発光層での発光を取り出すために、少なくとも一方の電極が透明でなくてはならず、通常酸化インジウムスズ(ITO)などの透明導電体で形成した透明電極を陽極として用いている。一方、電子注入を容易にして発光効率を上げるには、陰極に仕事関数の小さな物質を用いることが重要で、通常Mg−Ag、Al−Liなどの金属電極を用いている。   In an organic EL display device, in order to extract light emitted from the organic light emitting layer, at least one of the electrodes must be transparent, and a transparent electrode usually formed of a transparent conductor such as indium tin oxide (ITO) is used as an anode. It is used as. On the other hand, in order to facilitate electron injection and increase luminous efficiency, it is important to use a material having a small work function for the cathode, and usually metal electrodes such as Mg—Ag and Al—Li are used.

このような構成の有機EL表示装置において、有機発光層は、厚さ10nm程度ときわめて薄い膜で形成されている。このため、有機発光層も透明電極と同様、光をほぼ完全に透過する。その結果、非発光時に透明基板の表面から入射し、透明電極と有機発光層とを透過して金属電極で反射した光が、再び透明基板の表面側へと出るため、外部から視認したとき、有機EL表示装置の表示面が鏡面のように見える。   In the organic EL display device having such a configuration, the organic light emitting layer is formed of a very thin film having a thickness of about 10 nm. For this reason, the organic light emitting layer transmits light almost completely like the transparent electrode. As a result, light that is incident from the surface of the transparent substrate at the time of non-light emission, passes through the transparent electrode and the organic light emitting layer, and is reflected by the metal electrode is again emitted to the surface side of the transparent substrate. The display surface of the organic EL display device looks like a mirror surface.

電圧の印加によって発光する有機発光層の表面側に透明電極を備えるとともに、有機発光層の裏面側に金属電極を備えてなる有機エレクトロルミネセンス発光体を含む有機EL表示装置において、透明電極の表面側に偏光板を設けるとともに、これら透明電極と偏光板との間に位相差板を設けることができる。   In an organic EL display device comprising an organic electroluminescent light emitting device comprising a transparent electrode on the surface side of an organic light emitting layer that emits light upon application of a voltage and a metal electrode on the back side of the organic light emitting layer, the surface of the transparent electrode While providing a polarizing plate on the side, a retardation plate can be provided between the transparent electrode and the polarizing plate.

位相差板および偏光板は、外部から入射して金属電極で反射してきた光を偏光する作用を有するため、その偏光作用によって金属電極の鏡面を外部から視認させないという効果がある。特に、位相差板を1/4 波長板で構成し、かつ偏光板と位相差板との偏光方向のなす角をπ/4 に調整すれば、金属電極の鏡面を完全に遮蔽することができる。   Since the retardation plate and the polarizing plate have a function of polarizing light incident from the outside and reflected by the metal electrode, there is an effect that the mirror surface of the metal electrode is not visually recognized by the polarization action. In particular, the mirror surface of the metal electrode can be completely shielded by configuring the retardation plate with a quarter-wave plate and adjusting the angle formed by the polarization direction of the polarizing plate and the retardation plate to π / 4. .

すなわち、この有機EL表示装置に入射する外部光は、偏光板により直線偏光成分のみが透過する。この直線偏光は位相差板により一般に楕円偏光となるが、とくに位相差板が1/4 波長板でしかも偏光板と位相差板との偏光方向のなす角がπ/4 のときには円偏光となる。   That is, only the linearly polarized light component of the external light incident on the organic EL display device is transmitted by the polarizing plate. This linearly polarized light becomes generally elliptically polarized light by the phase difference plate, but becomes circularly polarized light especially when the phase difference plate is a quarter wave plate and the angle between the polarization direction of the polarizing plate and the phase difference plate is π / 4. .

この円偏光は、透明基板、透明電極、有機薄膜を透過し、金属電極で反射して、再び有機薄膜、透明電極、透明基板を透過して、位相差板に再び直線偏光となる。そして、この直線偏光は、偏光板の偏光方向と直交しているので、偏光板を透過できない。その結果、金属電極の鏡面を完全に遮蔽することができる。   This circularly polarized light is transmitted through the transparent substrate, the transparent electrode, and the organic thin film, is reflected by the metal electrode, is again transmitted through the organic thin film, the transparent electrode, and the transparent substrate, and becomes linearly polarized light again on the retardation plate. And since this linearly polarized light is orthogonal to the polarization direction of a polarizing plate, it cannot permeate | transmit a polarizing plate. As a result, the mirror surface of the metal electrode can be completely shielded.

以下に、実施例によって本発明を具体的に説明するが、本発明はこれら実施例によって限定されるものではない。なお、各例中の部および%はいずれも重量基準である。   EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, all the parts and% in each example are based on weight.

(重量平均分子量の測定)
作製した(メタ)アクリル系ポリマーの重量平均分子量は、GPC(ゲル・パーミエーション・クロマトグラフィ)にて測定し、標準ポリスチレンにより換算した。
GPC装置:東ソー社製、HLC−8120GPC
カラム:東ソー社製、G7000HXL+GMHXL+GMHXL
カラムサイズ:7.8mmφ×30cm×3(合計90cm)
流量:0.8ml/min
濃度:0.1wt%
注入量:100μl
カラム温度:40℃
溶離液:THF
検出器:示差屈折計

(分子量10万以下のポリマー成分の含有率測定)
分子量10万以下のポリマー成分の含有率は、上記GPCの測定結果からデータ処理装置(東ソー社製、GPC−8020)を用いて算出した。ただし、モノマー成分は除外した。
(Measurement of weight average molecular weight)
The weight average molecular weight of the produced (meth) acrylic polymer was measured by GPC (gel permeation chromatography) and converted by standard polystyrene.
GPC device: manufactured by Tosoh Corporation, HLC-8120GPC
Column: manufactured by Tosoh Corporation, G7000H XL + GMH XL + GMH XL
Column size: 7.8 mmφ × 30 cm × 3 (total 90 cm)
Flow rate: 0.8ml / min
Concentration: 0.1 wt%
Injection volume: 100 μl
Column temperature: 40 ° C
Eluent: THF
Detector: Differential refractometer

(Measurement of content of polymer component having a molecular weight of 100,000 or less)
The content of the polymer component having a molecular weight of 100,000 or less was calculated from the GPC measurement result using a data processing device (GPC-8020, manufactured by Tosoh Corporation). However, the monomer component was excluded.

(光学部材用粘着剤組成物の粘度測定)
光学部材用粘着剤組成物の粘度は、TV−20粘度計スピンドルタイプ(東機産業株式会社)を用いて下記の条件で測定した。
ローター:THH−14
回転数:10rpm
ずり速度:2.5/s
測定温度:23℃

(光学部材用粘着剤組成物の塗工性評価)
光学部材用粘着剤組成物の塗工性は、粘度と表面均一性で評価した。評価結果を表1に示す。
粘度:上記粘度測定で、10000mPa・s未満の場合を○(良)、10000mPa・s以上の場合を×(不良)とした。
表面均一性:塗工の際に、ポリマーの析出がなく、均一な塗工面が形成できた場合を○、ポリマーが析出し、均一な塗工面が形成できない場合を×とした。
(Measurement of viscosity of pressure-sensitive adhesive composition for optical members)
The viscosity of the pressure-sensitive adhesive composition for optical members was measured under the following conditions using a TV-20 viscometer spindle type (Toki Sangyo Co., Ltd.).
Rotor: THH-14
Rotation speed: 10rpm
Shear rate: 2.5 / s
Measurement temperature: 23 ° C

(Coating property evaluation of pressure-sensitive adhesive composition for optical members)
The coating property of the pressure-sensitive adhesive composition for optical members was evaluated by viscosity and surface uniformity. The evaluation results are shown in Table 1.
Viscosity: In the above viscosity measurement, the case of less than 10000 mPa · s was evaluated as “good” and the case of 10000 mPa · s or more was evaluated as “x” (bad).
Surface uniformity: In the case of coating, the case where no polymer was precipitated and a uniform coated surface could be formed was evaluated as ◯, and the case where the polymer was deposited and a uniform coated surface could not be formed was evaluated as x.

(粘着型光学部材の耐久性評価)
得られた粘着型光学部材(15インチサイズ、240×320mm)を無アルカリガラス(コーニング1737、250×350mm、厚み0.7mm)に貼り付けてサンプルを作製した。該サンプルを50℃、0.5MPaのオートクレーブ中で15分間保存した。その後、該サンプルを80℃の環境下で500時間保存し、さらに60℃、90%RHの環境下で500時間保存した。その後、該サンプルを用いて下記基準で粘着型光学部材の耐久性評価を行った。評価結果を表1に示す。
○:光学部材の剥がれや浮きがない。
×:光学部材の剥がれや浮きがある。
(Durability evaluation of adhesive optical members)
The obtained adhesive optical member (15 inch size, 240 × 320 mm) was attached to non-alkali glass (Corning 1737, 250 × 350 mm, thickness 0.7 mm) to prepare a sample. The sample was stored in an autoclave at 50 ° C. and 0.5 MPa for 15 minutes. Thereafter, the sample was stored in an environment of 80 ° C. for 500 hours, and further stored in an environment of 60 ° C. and 90% RH for 500 hours. Then, durability evaluation of the adhesion type optical member was performed on the following reference | standard using this sample. The evaluation results are shown in Table 1.
○: There is no peeling or floating of the optical member.
X: There is peeling or floating of the optical member.

実施例1
(光学部材用粘着剤組成物の調製)
ブチルアクリレート70部、2−エチルへキシルアクリレート25部、アクリル酸5部、2−ヒドロキシエチルアクリレート0.08部、2,2−アゾビスイソブチロニトリル0.1部、及び酢酸エチル160部を窒素導入管、冷却管を備えた4つ口フラスコに投入し、充分に窒素置換した後、窒素気流下で撹拌しながら55℃で10時間重合反応を行い、重量平均分子量220万、分子量10万以下のポリマー成分の含有率が2重量%であるアクリル系ポリマーを含有する溶液(1)(固形分濃度:37重量%)を得た。
Example 1
(Preparation of pressure-sensitive adhesive composition for optical members)
70 parts of butyl acrylate, 25 parts of 2-ethylhexyl acrylate, 5 parts of acrylic acid, 0.08 part of 2-hydroxyethyl acrylate, 0.1 part of 2,2-azobisisobutyronitrile, and 160 parts of ethyl acetate After putting into a four-necked flask equipped with a nitrogen introduction tube and a cooling tube and sufficiently purging with nitrogen, a polymerization reaction was carried out at 55 ° C. for 10 hours with stirring under a nitrogen stream, and a weight average molecular weight of 2.2 million and a molecular weight of 100,000 The solution (1) (solid content concentration: 37 weight%) containing the acrylic polymer whose content rate of the following polymer components is 2 weight% was obtained.

該溶液(1)にヘプタン(溶解度パラメータ:7.3)327.3部、トルエン(溶解度パラメータ:8.9)27.3部、及び酢酸エチル(溶解度パラメータ:9.1)30.9部を加えて溶液(2)(固形分濃度:15重量%)を得た。該溶液(2)中の炭化水素系溶媒A(ヘプタン)の含有量は全有機溶媒の60%であり、高沸点高溶解性溶媒B(トルエン)の含有量は全有機溶媒の5%である。   In this solution (1), 327.3 parts of heptane (solubility parameter: 7.3), 27.3 parts of toluene (solubility parameter: 8.9), and 30.9 parts of ethyl acetate (solubility parameter: 9.1) were added. In addition, a solution (2) (solid content concentration: 15% by weight) was obtained. The content of the hydrocarbon solvent A (heptane) in the solution (2) is 60% of the total organic solvent, and the content of the high boiling point high solubility solvent B (toluene) is 5% of the total organic solvent. .

溶液(2)のポリマー固形分100部に対して、シランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1部、トリメチロールプロパンのトリレンジイソシアネート付加物からなるポリイソシアネート系架橋剤0.5部を溶液(2)に加えて均一に混合して光学部材用粘着剤組成物aを調製した。
(粘着型光学部材の作成)
シリコーン剥離処理したポリエチレンテレフタレートフィルム(厚さ:38μm)に、上記粘着剤組成物aを乾燥後の厚さが25μmになるように塗布し、140℃で2分間加熱して光学部材用粘着剤層を形成した。該光学部材用粘着剤層を偏光板に貼り合わせて粘着型光学部材を作成した。
Polyisocyanate-based crosslinking agent 0 comprising 0.1 part of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent and a tolylene diisocyanate adduct of trimethylolpropane with respect to 100 parts of polymer solids of the solution (2) .5 parts was added to the solution (2) and mixed uniformly to prepare a pressure-sensitive adhesive composition a for optical members.
(Creation of adhesive optical member)
The pressure-sensitive adhesive composition a was applied to a polyethylene terephthalate film (thickness: 38 μm) subjected to silicone release treatment so that the thickness after drying was 25 μm, and heated at 140 ° C. for 2 minutes to be a pressure-sensitive adhesive layer for optical members Formed. The pressure-sensitive adhesive layer for an optical member was bonded to a polarizing plate to prepare an adhesive optical member.

実施例2
(光学部材用粘着剤組成物の調製)
前記溶液(1)にヘプタン245.5部、トルエン109.1部、及び酢酸エチル30.9部を加えて溶液(3)(固形分濃度:15重量%)を得た。該溶液(3)中の炭化水素系溶媒A(ヘプタン)の含有量は全有機溶媒の45%であり、高沸点高溶解性溶媒B(トルエン)の含有量は全有機溶媒の20%である。
Example 2
(Preparation of pressure-sensitive adhesive composition for optical members)
245.5 parts of heptane, 109.1 parts of toluene, and 30.9 parts of ethyl acetate were added to the solution (1) to obtain a solution (3) (solid content concentration: 15% by weight). The content of the hydrocarbon solvent A (heptane) in the solution (3) is 45% of the total organic solvent, and the content of the high boiling point high solubility solvent B (toluene) is 20% of the total organic solvent. .

溶液(3)のポリマー固形分100部に対して、シランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1部、トリメチロールプロパンのトリレンジイソシアネート付加物からなるポリイソシアネート系架橋剤0.5部を溶液(3)に加えて均一に混合して光学部材用粘着剤組成物bを調製した。
(粘着型光学部材の作成)
上記光学部材用粘着剤組成物bを用いた以外は実施例1と同様の方法で粘着型光学部材を作成した。
Polyisocyanate-based crosslinking agent 0 comprising 0.1 part of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent and a tolylene diisocyanate adduct of trimethylolpropane with respect to 100 parts of polymer solids of the solution (3) .5 parts was added to the solution (3) and mixed uniformly to prepare an optical member pressure-sensitive adhesive composition b.
(Creation of adhesive optical member)
An adhesive optical member was prepared in the same manner as in Example 1 except that the optical member adhesive composition b was used.

実施例3
(光学部材用粘着剤組成物の調製)
前記溶液(1)にヘプタン190.9部、トルエン27.3部、及び酢酸エチル30.9部を加えて溶液(4)(固形分濃度:15重量%)を得た。該溶液(4)中の炭化水素系溶媒A(ヘプタン)の含有量は全有機溶媒の35%であり、高沸点高溶解性溶媒B(トルエン)の含有量は全有機溶媒の5%である。
Example 3
(Preparation of pressure-sensitive adhesive composition for optical members)
190.9 parts of heptane, 27.3 parts of toluene, and 30.9 parts of ethyl acetate were added to the solution (1) to obtain a solution (4) (solid content concentration: 15% by weight). The content of the hydrocarbon solvent A (heptane) in the solution (4) is 35% of the total organic solvent, and the content of the high boiling point high solubility solvent B (toluene) is 5% of the total organic solvent. .

溶液(4)のポリマー固形分100部に対して、シランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1部、トリメチロールプロパンのトリレンジイソシアネート付加物からなるポリイソシアネート系架橋剤0.5部を溶液(4)に加えて均一に混合して光学部材用粘着剤組成物cを調製した。
(粘着型光学部材の作成)
上記光学部材用粘着剤組成物cを用いた以外は実施例1と同様の方法で粘着型光学部材を作成した。
Polyisocyanate-based crosslinking agent 0 comprising 0.1 part of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent and a tolylene diisocyanate adduct of trimethylolpropane with respect to 100 parts of polymer solids of the solution (4) .5 parts was added to the solution (4) and mixed uniformly to prepare an optical member pressure-sensitive adhesive composition c.
(Creation of adhesive optical member)
An adhesive optical member was prepared in the same manner as in Example 1 except that the optical member adhesive composition c was used.

実施例4
(光学部材用粘着剤組成物の調製)
前記溶液(1)にヘプタン109.1部、トルエン245.5部、及び酢酸エチル30.9部を加えて溶液(5)(固形分濃度:15重量%)を得た。該溶液(5)中の炭化水素系溶媒A(ヘプタン)の含有量は全有機溶媒の20%であり、高沸点高溶解性溶媒B(トルエン)の含有量は全有機溶媒の45%である。
Example 4
(Preparation of pressure-sensitive adhesive composition for optical members)
To the solution (1), 109.1 parts of heptane, 245.5 parts of toluene, and 30.9 parts of ethyl acetate were added to obtain a solution (5) (solid content concentration: 15% by weight). The content of the hydrocarbon solvent A (heptane) in the solution (5) is 20% of the total organic solvent, and the content of the high boiling point high solubility solvent B (toluene) is 45% of the total organic solvent. .

溶液(5)のポリマー固形分100部に対して、シランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1部、トリメチロールプロパンのトリレンジイソシアネート付加物からなるポリイソシアネート系架橋剤0.5部を溶液(5)に加えて均一に混合して光学部材用粘着剤組成物dを調製した。
(粘着型光学部材の作成)
上記光学部材用粘着剤組成物dを用いた以外は実施例1と同様の方法で粘着型光学部材を作成した。
Polyisocyanate-based crosslinking agent 0 comprising 0.1 part of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent and a tolylene diisocyanate adduct of trimethylolpropane with respect to 100 parts of the polymer solid content of the solution (5) 0 .5 parts was added to the solution (5) and mixed uniformly to prepare an optical member pressure-sensitive adhesive composition d.
(Creation of adhesive optical member)
A pressure-sensitive adhesive optical member was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition d for optical members was used.

実施例5
(光学部材用粘着剤組成物の調製)
前記溶液(1)にヘキサン(溶解度パラメータ:7.3)245.5部、トルエン109.1部、及び酢酸エチル30.9部を加えて溶液(6)(固形分濃度:15重量%)を得た。該溶液(6)中の炭化水素系溶媒A(ヘキサン)の含有量は全有機溶媒の45%であり、高沸点高溶解性溶媒B(酢酸エチル+トルエン)の含有量は全有機溶媒の55%である。
Example 5
(Preparation of pressure-sensitive adhesive composition for optical members)
245.5 parts of hexane (solubility parameter: 7.3), 109.1 parts of toluene, and 30.9 parts of ethyl acetate are added to the solution (1) to obtain a solution (6) (solid content concentration: 15% by weight). Obtained. The content of the hydrocarbon solvent A (hexane) in the solution (6) is 45% of the total organic solvent, and the content of the high boiling point high solubility solvent B (ethyl acetate + toluene) is 55% of the total organic solvent. %.

溶液(6)のポリマー固形分100部に対して、シランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1部、トリメチロールプロパンのトリレンジイソシアネート付加物からなるポリイソシアネート系架橋剤0.5部を溶液(6)に加えて均一に混合して光学部材用粘着剤組成物eを調製した。
(粘着型光学部材の作成)
上記光学部材用粘着剤組成物eを用いた以外は実施例1と同様の方法で粘着型光学部材を作成した。
Polyisocyanate-based crosslinking agent 0 comprising 0.1 part of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent and a tolylene diisocyanate adduct of trimethylolpropane with respect to 100 parts of the polymer solid content of the solution (6) .5 parts was added to the solution (6) and mixed uniformly to prepare an optical member pressure-sensitive adhesive composition e.
(Creation of adhesive optical member)
A pressure-sensitive adhesive optical member was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition e for optical members was used.

実施例6
(光学部材用粘着剤組成物の調製)
前記溶液(1)にカクタスソルベント(ジャパンエナジー社製)245.5部、トルエン109.1部、及び酢酸エチル30.9部を加えて溶液(7)(固形分濃度:15重量%)を得た。該溶液(7)中の炭化水素系溶媒A(カクタスソルベント)の含有量は全有機溶媒の45%であり、高沸点高溶解性溶媒B(トルエン)の含有量は全有機溶媒の20%である。
Example 6
(Preparation of pressure-sensitive adhesive composition for optical members)
245.5 parts of Cactus solvent (manufactured by Japan Energy), 109.1 parts of toluene, and 30.9 parts of ethyl acetate are added to the solution (1) to obtain a solution (7) (solid content concentration: 15% by weight). It was. The content of the hydrocarbon solvent A (Cactus solvent) in the solution (7) is 45% of the total organic solvent, and the content of the high-boiling and highly soluble solvent B (toluene) is 20% of the total organic solvent. is there.

溶液(7)のポリマー固形分100部に対して、シランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1部、トリメチロールプロパンのトリレンジイソシアネート付加物からなるポリイソシアネート系架橋剤0.5部を溶液(7)に加えて均一に混合して光学部材用粘着剤組成物fを調製した。
(粘着型光学部材の作成)
上記光学部材用粘着剤組成物fを用いた以外は実施例1と同様の方法で粘着型光学部材を作成した。
Polyisocyanate-based crosslinking agent 0 comprising 0.1 part of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent and a tolylene diisocyanate adduct of trimethylolpropane with respect to 100 parts of polymer solids of the solution (7) .5 parts was added to the solution (7) and mixed uniformly to prepare a pressure-sensitive adhesive composition f for optical members.
(Creation of adhesive optical member)
A pressure-sensitive adhesive optical member was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition f for optical members was used.

実施例7
(光学部材用粘着剤組成物の調製)
ブチルアクリレート100部、アクリル酸5部、2−ヒドロキシエチルアクリレート0.07部、ジベンゾイルパーオキシド0.2部、及び酢酸エチル160部を窒素導入管、冷却管を備えた4つ口フラスコに投入し、充分に窒素置換した後、窒素気流下で撹拌しながら58℃で10時間重合反応を行い、重量平均分子量200万、分子量10万以下のポリマー成分の含有率が2重量%であるアクリル系ポリマーを含有する溶液(8)(固形分濃度:37重量%)を得た。
Example 7
(Preparation of pressure-sensitive adhesive composition for optical members)
100 parts of butyl acrylate, 5 parts of acrylic acid, 0.07 part of 2-hydroxyethyl acrylate, 0.2 part of dibenzoyl peroxide and 160 parts of ethyl acetate are put into a four-necked flask equipped with a nitrogen introduction tube and a cooling tube. Then, after sufficiently purging with nitrogen, a polymerization reaction is carried out at 58 ° C. for 10 hours with stirring under a nitrogen stream, and the content of the polymer component having a weight average molecular weight of 2 million and a molecular weight of 100,000 or less is 2% by weight. A solution (8) containing polymer (solid content concentration: 37% by weight) was obtained.

該溶液(8)にヘプタン250.5部、トルエン111.3部、及び酢酸エチル34.8部を加えて溶液(9)(固形分濃度:15重量%)を得た。該溶液(9)中の炭化水素系溶媒A(ヘプタン)の含有量は全有機溶媒の45%であり、高沸点高溶解性溶媒B(トルエン)の含有量は全有機溶媒の20%である。   250.5 parts of heptane, 111.3 parts of toluene, and 34.8 parts of ethyl acetate were added to the solution (8) to obtain a solution (9) (solid content concentration: 15% by weight). The content of the hydrocarbon solvent A (heptane) in the solution (9) is 45% of the total organic solvent, and the content of the high boiling point high solubility solvent B (toluene) is 20% of the total organic solvent. .

溶液(9)のポリマー固形分100部に対して、シランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.075部、トリメチロールプロパンのトリレンジイソシアネート付加物からなるポリイソシアネート系架橋剤0.6部を溶液(9)に加えて均一に混合して光学部材用粘着剤組成物gを調製した。
(粘着型光学部材の作成)
上記光学部材用粘着剤組成物gを用いた以外は実施例1と同様の方法で粘着型光学部材を作成した。
Polyisocyanate-based crosslinking agent 0 comprising 0.075 part of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent and a tolylene diisocyanate adduct of trimethylolpropane with respect to 100 parts of polymer solids of the solution (9) .6 parts was added to the solution (9) and mixed uniformly to prepare a pressure-sensitive adhesive composition g for optical members.
(Creation of adhesive optical member)
An adhesive optical member was prepared in the same manner as in Example 1 except that the above adhesive composition g for optical members was used.

比較例1
(光学部材用粘着剤組成物の調製)
前記溶液(1)に酢酸エチル546部を加えて溶液(10)(固形分濃度:12重量%)を得た。
Comparative Example 1
(Preparation of pressure-sensitive adhesive composition for optical members)
546 parts of ethyl acetate was added to the solution (1) to obtain a solution (10) (solid content concentration: 12% by weight).

溶液(10)のポリマー固形分100部に対して、シランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1部、トリメチロールプロパンのトリレンジイソシアネート付加物からなるポリイソシアネート系架橋剤0.5部を溶液(10)に加えて均一に混合して光学部材用粘着剤組成物hを調製した。
(粘着型光学部材の作成)
上記光学部材用粘着剤組成物hを用いた以外は実施例1と同様の方法で粘着型光学部材を作成した。
Polyisocyanate-based cross-linking agent comprising 0.1 part of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent and a tolylene diisocyanate adduct of trimethylolpropane with respect to 100 parts of polymer solids of the solution (10) 0 .5 parts was added to the solution (10) and mixed uniformly to prepare an optical member pressure-sensitive adhesive composition h.
(Creation of adhesive optical member)
An adhesive optical member was prepared in the same manner as in Example 1 except that the optical member pressure-sensitive adhesive composition h was used.

比較例2
(光学部材用粘着剤組成物の調製)
前記溶液(1)に酢酸エチル385.5部を加えて溶液(11)(固形分濃度:15重量%)を得た。
Comparative Example 2
(Preparation of pressure-sensitive adhesive composition for optical members)
385.5 parts of ethyl acetate was added to the solution (1) to obtain a solution (11) (solid content concentration: 15% by weight).

溶液(11)のポリマー固形分100部に対して、シランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1部、トリメチロールプロパンのトリレンジイソシアネート付加物からなるポリイソシアネート系架橋剤0.5部を溶液(11)に加えて均一に混合して光学部材用粘着剤組成物iを調製した。
(粘着型光学部材の作成)
上記光学部材用粘着剤組成物iを用いた以外は実施例1と同様の方法で粘着型光学部材を作成した。
Polyisocyanate-based crosslinking agent 0 comprising 0.1 part of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent and a tolylene diisocyanate adduct of trimethylolpropane with respect to 100 parts of polymer solids of the solution (11) .5 parts was added to the solution (11) and mixed uniformly to prepare an optical member pressure-sensitive adhesive composition i.
(Creation of adhesive optical member)
A pressure-sensitive adhesive optical member was prepared in the same manner as in Example 1 except that the above-mentioned pressure-sensitive adhesive composition i for optical members was used.

比較例3
(光学部材用粘着剤組成物の調製)
前記溶液(1)にヘプタン354.6部、トルエン27.3部、及び酢酸エチル3.7部を加えて溶液(12)(固形分濃度:15重量%)を得た。該溶液(12)中の炭化水素系溶媒A(ヘプタン)の含有量は全有機溶媒の65%であり、高沸点高溶解性溶媒B(トルエン)の含有量は全有機溶媒の5%である。
Comparative Example 3
(Preparation of pressure-sensitive adhesive composition for optical members)
To the solution (1), 354.6 parts of heptane, 27.3 parts of toluene, and 3.7 parts of ethyl acetate were added to obtain a solution (12) (solid content concentration: 15% by weight). The content of the hydrocarbon solvent A (heptane) in the solution (12) is 65% of the total organic solvent, and the content of the high boiling point high solubility solvent B (toluene) is 5% of the total organic solvent. .

溶液(12)のポリマー固形分100部に対して、シランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1部、トリメチロールプロパンのトリレンジイソシアネート付加物からなるポリイソシアネート系架橋剤0.5部を溶液(12)に加えて均一に混合して光学部材用粘着剤組成物jを調製した。
(粘着型光学部材の作成)
上記光学部材用粘着剤組成物jを用いた以外は実施例1と同様の方法で粘着型光学部材を作成した。
Polyisocyanate-based crosslinking agent 0 comprising 0.1 part of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent and a tolylene diisocyanate adduct of trimethylolpropane with respect to 100 parts of polymer solids of the solution (12) .5 parts was added to the solution (12) and mixed uniformly to prepare an optical member pressure-sensitive adhesive composition j.
(Creation of adhesive optical member)
A pressure-sensitive adhesive optical member was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition j for optical members was used.

比較例4
(光学部材用粘着剤組成物の調製)
前記溶液(1)にヘプタン327.3部、及び酢酸エチル58.2部を加えて溶液(13)(固形分濃度:15重量%)を得た。該溶液(13)中の炭化水素系溶媒A(ヘプタン)の含有量は全有機溶媒の60%である。
Comparative Example 4
(Preparation of pressure-sensitive adhesive composition for optical members)
327.3 parts of heptane and 58.2 parts of ethyl acetate were added to the solution (1) to obtain a solution (13) (solid content concentration: 15% by weight). The content of the hydrocarbon solvent A (heptane) in the solution (13) is 60% of the total organic solvent.

溶液(13)のポリマー固形分100部に対して、シランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1部、トリメチロールプロパンのトリレンジイソシアネート付加物からなるポリイソシアネート系架橋剤0.5部を溶液(13)に加えて均一に混合して光学部材用粘着剤組成物kを調製した。
(粘着型光学部材の作成)
上記光学部材用粘着剤組成物kを用いた以外は実施例1と同様の方法で粘着型光学部材を作成した。
Polyisocyanate-based crosslinking agent 0 comprising 0.1 part of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent and a tolylene diisocyanate adduct of trimethylolpropane with respect to 100 parts of polymer solids of the solution (13) .5 parts was added to the solution (13) and mixed uniformly to prepare an optical member pressure-sensitive adhesive composition k.
(Creation of adhesive optical member)
A pressure-sensitive adhesive optical member was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition k for optical members was used.

比較例5
(光学部材用粘着剤組成物の調製)
前記溶液(1)にヘプタン54.6部、トルエン109.1部、及び酢酸エチル221.9部を加えて溶液(14)(固形分濃度:15重量%)を得た。該溶液(14)中の炭化水素系溶媒A(ヘプタン)の含有量は全有機溶媒の10%であり、高沸点高溶解性溶媒B(トルエン)の含有量は全有機溶媒の20%である。
Comparative Example 5
(Preparation of pressure-sensitive adhesive composition for optical members)
To the solution (1), 54.6 parts of heptane, 109.1 parts of toluene, and 221.9 parts of ethyl acetate were added to obtain a solution (14) (solid content concentration: 15% by weight). The content of the hydrocarbon solvent A (heptane) in the solution (14) is 10% of the total organic solvent, and the content of the high boiling point high solubility solvent B (toluene) is 20% of the total organic solvent. .

溶液(14)のポリマー固形分100部に対して、シランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1部、トリメチロールプロパンのトリレンジイソシアネート付加物からなるポリイソシアネート系架橋剤0.5部を溶液(14)に加えて均一に混合して光学部材用粘着剤組成物lを調製した。
(粘着型光学部材の作成)
上記光学部材用粘着剤組成物lを用いた以外は実施例1と同様の方法で粘着型光学部材を作成した。
Polyisocyanate-based crosslinking agent 0 comprising 0.1 part of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent and a tolylene diisocyanate adduct of trimethylolpropane with respect to 100 parts of polymer solids of the solution (14) .5 parts was added to the solution (14) and mixed uniformly to prepare an optical member pressure-sensitive adhesive composition l.
(Creation of adhesive optical member)
A pressure-sensitive adhesive optical member was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition 1 for optical members was used.

比較例6
(光学部材用粘着剤組成物の調製)
前記溶液(1)にデカン(溶解度パラメータ:6.6)245.5部、トルエン109.1部、及び酢酸エチル30.9部を加えて溶液(15)(固形分濃度:15重量%)を得た。該溶液(15)中のデカンの含有量は全有機溶媒の45%である。
Comparative Example 6
(Preparation of pressure-sensitive adhesive composition for optical members)
To the solution (1), 245.5 parts of decane (solubility parameter: 6.6), 109.1 parts of toluene, and 30.9 parts of ethyl acetate were added to obtain a solution (15) (solid content concentration: 15% by weight). Obtained. The decane content in the solution (15) is 45% of the total organic solvent.

溶液(15)のポリマー固形分100部に対して、シランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1部、トリメチロールプロパンのトリレンジイソシアネート付加物からなるポリイソシアネート系架橋剤0.5部を溶液(15)に加えて均一に混合して光学部材用粘着剤組成物mを調製した。
(粘着型光学部材の作成)
上記光学部材用粘着剤組成物mを用いた以外は実施例1と同様の方法で粘着型光学部材を作成した。
Polyisocyanate-based crosslinking agent 0 comprising 0.1 part of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent and a tolylene diisocyanate adduct of trimethylolpropane with respect to 100 parts of polymer solids of the solution (15) .5 parts was added to the solution (15) and mixed uniformly to prepare an optical member pressure-sensitive adhesive composition m.
(Creation of adhesive optical member)
A pressure-sensitive adhesive optical member was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition m for optical members was used.

比較例7
前記溶液(8)に酢酸エチル396.6部を加えて溶液(16)(固形分濃度:15重量%)を得た。
Comparative Example 7
396.6 parts of ethyl acetate was added to the solution (8) to obtain a solution (16) (solid content concentration: 15% by weight).

溶液(16)のポリマー固形分100部に対して、シランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1部、トリメチロールプロパンのトリレンジイソシアネート付加物からなるポリイソシアネート系架橋剤0.5部を溶液(16)に加えて均一に混合して光学部材用粘着剤組成物nを調製した。
(粘着型光学部材の作成)
上記光学部材用粘着剤組成物nを用いた以外は実施例1と同様の方法で粘着型光学部材を作成した。
Polyisocyanate-based crosslinking agent 0 comprising 0.1 part of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent and a tolylene diisocyanate adduct of trimethylolpropane with respect to 100 parts of polymer solids of the solution (16) .5 parts was added to the solution (16) and mixed uniformly to prepare an optical member pressure-sensitive adhesive composition n.
(Creation of adhesive optical member)
A pressure-sensitive adhesive optical member was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition n for optical members was used.

Figure 0004727238
表1から明らかなように、実施例1〜7では、有機溶媒の使用量削減が可能になり、塗工性に優れる光学部材用粘着剤組成物が得られる。また、該光学部材用粘着剤組成物から形成される粘着剤層は、耐久性及び表面均一性に優れることがわかる。
Figure 0004727238
As is clear from Table 1, in Examples 1 to 7, the amount of the organic solvent used can be reduced, and a pressure-sensitive adhesive composition for an optical member having excellent coating properties can be obtained. Moreover, it turns out that the adhesive layer formed from this adhesive composition for optical members is excellent in durability and surface uniformity.

Claims (7)

(メタ)アクリル系ポリマー、炭素数6〜9の脂肪族炭化水素系溶媒(A)、及び前記脂肪族炭化水素系溶媒よりも沸点が高くかつ前記脂肪族炭化水素系溶媒よりも(メタ)アクリル系ポリマーの溶解性が高い高沸点高溶解性溶媒(B)を含有しており、前記脂肪族炭化水素系溶媒(A)の含有量が全有機溶媒の20〜60重量%であり、かつ前記高沸点高溶解性溶媒(B)の含有量(重量%)に対する前記脂肪族炭化水素系溶媒(A)の含有量(重量%)の比(高沸点高溶解性溶媒(B)/脂肪族炭化水素系溶媒(A))が0.05〜4である光学部材用粘着剤組成物。 (Meth) acrylic polymer, of 6 to 9 carbon atoms aliphatic hydrocarbon solvent (A), and the aliphatic boiling point than high hydrocarbon solvent and than said aliphatic hydrocarbon solvent (meth) acrylate A high-boiling and high-solubility solvent (B) having high solubility of the polymer, the content of the aliphatic hydrocarbon solvent (A) is 20 to 60% by weight of the total organic solvent, and Ratio of the content (% by weight) of the aliphatic hydrocarbon solvent (A) to the content (% by weight) of the high boiling point high solubility solvent (B) (high boiling point high solubility solvent (B) / aliphatic carbonization The adhesive composition for optical members whose hydrogen-based solvent (A)) is 0.05-4. (メタ)アクリル系ポリマーは、モノマーとして炭素数2〜4のアルキル基を有するアクリル酸アルキルを60重量%以上含有してなり、重量平均分子量が150万以上であり、かつ分子量10万以下のポリマー成分の含有率が20重量%以下である請求項1記載の光学部材用粘着剤組成物。 The (meth) acrylic polymer contains 60% by weight or more of an alkyl acrylate having an alkyl group having 2 to 4 carbon atoms as a monomer, has a weight average molecular weight of 1,500,000 or more, and a molecular weight of 100,000 or less. The pressure-sensitive adhesive composition for an optical member according to claim 1, wherein the content of the component is 20% by weight or less. (メタ)アクリル系ポリマーは、さらに、モノマーとして不飽和カルボン酸を0.2〜7重量%含有してなる請求項2記載の光学部材用粘着剤組成物。 The pressure-sensitive adhesive composition for an optical member according to claim 2, wherein the (meth) acrylic polymer further contains 0.2 to 7% by weight of an unsaturated carboxylic acid as a monomer. (メタ)アクリル系ポリマー100重量部に対して、シランカップリング剤を0.01〜1重量部含有する請求項1〜3のいずれかに記載の光学部材用粘着剤組成物。 The pressure-sensitive adhesive composition for an optical member according to any one of claims 1 to 3, comprising 0.01 to 1 part by weight of a silane coupling agent with respect to 100 parts by weight of the (meth) acrylic polymer. (メタ)アクリル系ポリマー100重量部に対して、架橋剤を0.1〜5重量部含有する請求項1〜4のいずれかに記載の光学部材用粘着剤組成物。 The pressure-sensitive adhesive composition for an optical member according to any one of claims 1 to 4, comprising 0.1 to 5 parts by weight of a crosslinking agent with respect to 100 parts by weight of the (meth) acrylic polymer. 請求項1〜5のいずれかに記載の光学部材用粘着剤組成物を用いて、粘着剤層を形成する光学部材用粘着剤層の製造方法。The manufacturing method of the adhesive layer for optical members which forms an adhesive layer using the adhesive composition for optical members in any one of Claims 1-5. 請求項1〜5いずれかに記載の光学部材用粘着剤組成物を用いて、光学部材の片面または両面に粘着剤層を形成する粘着剤型光学部材の製造方法。The manufacturing method of the adhesive type optical member which forms an adhesive layer in the single side | surface or both surfaces of an optical member using the adhesive composition for optical members in any one of Claims 1-5.
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